Catalysts and methods for catalytic oxidation

ABSTRACT

Catalytic systems and methods for oxidizing materials in the presence of metal catalysts (preferably manganese-containing catalysts) complexed with selected macropolycyclic rigid ligands, preferably cross-bridged macropolycyclic ligands. Included are using these metal catalysts in such processes as: synthetic organic oxidation reactions such as oxidation of organic functional groups, hydrocarbons, and heteroatoms, including enantiomeric epoxidation of alkenes, enynes, sulfides to sulfones and the like; oxidation of oxidizable compounds (e.g., stains) on surfaces such as fabrics, dishes, countertops, dentures and the like; oxidation of oxidizable compounds in solution, dye transfer inhibition in the laundering of fabrics; and further in the bleaching of pulp and paper products.

CROSS-REFERENCE

This application is a continuation of and claims priority under 35U.S.C. § 120 to U.S. application Ser. No. 10/228,854, filed Aug. 27,2002, which in turn claims priority to U.S. application Ser. No.10/155,105, filed May 24, 2002, (now abandoned) which in turn claimspriority to U.S. application Ser. No. 09/380,672, filed Sep. 7, 1999,(now abandoned) which is an entry into the U.S. National Stage under 35U.S.C. § 371 of PCT International Application Serial No. PCT/IB98/00302,filed Mar. 6, 1998, which claims priority under PCT Article 8 and 35U.S.C. § 119(e) to U.S. Provisional Application Ser. No. 60/040,629,filed Mar. 7, 1997 (now abandoned).

TECHNICAL FIELD

The present invention relates to catalytic systems and methods foroxidizing materials in the presence of catalysts which are complexes oftransition metals such as Mn, Fe or Cr, with selected macropolycyclicrigid ligands, preferably cross-bridged macropolycyclic ligands. Morespecifically, the present invention relates to catalytic oxidation ofoxidizable compounds using said metal catalysts, including syntheticorganic oxidation reactions as appropriate to chemical process industry,drug synthesis, and the preparation of specialty chemicals, such asenantiomeric epoxidation of alkenes, oxidation of organic functionalgroups, hydrocarbons, heteroatoms, or enynes, conversion of sulfides tosulfones, and the like; oxidation of oxidizable compounds (e.g., stains)on surfaces such as fabrics, dishes, countertops, dentures and the like;oxidation of oxidizable compounds in solution; dye transfer inhibitionin the laundering of fabrics; the decontamination of soils; and further,to the bleaching of pulp and paper. Preferred catalytic systems includetransition-metal complexes of ligands which are polyazamacropolycycles,especially including specific azamacrobicycles, such as cross-bridgedderivatives of cyclam.

BACKGROUND OF THE INVENTION

A damaging effect of manganese on fabrics during bleaching has beenknown since the 19th century. In the 1960's and ‘70's, efforts were madeto include simple Mn(II) salts in detergents, but none saw commercialsuccess. More recently, metal-containing catalysts containingmacrocyclic ligands have been described for use in bleachingcompositions. Such catalysts include those described asmanganese-containing derivatives of small macrocycles, especially1,4,7-trimethyl-1,4,7-triazacyclononane. These catalysts assertedlycatalyze the bleaching action of peroxy compounds against variousstains. Several are said to be effective in washing and bleaching ofsubstrates, including in laundry and cleaning applications and in thetextile, paper and wood pulp industries. However, such metal-containingbleach catalysts, especially these manganese-containing catalysts, stillhave shortcomings, for example a tendency to damage textile fabric,relatively high cost, high color, and the ability to locally stain ordiscolor substrates.

Salts of cationic-metal dry cave complexes have been described in U.S.Pat. No. 4,888,032, to Busch, Dec. 19, 1989 as complexing oxygenreversibly, and are taught as being useful for oxygen scavenging andseparating oxygen from air. A wide variety of ligands are taught to beusable, some of which include macrocycle ring structures and bridginggroups. See also: D. H. Busch, Chemical Reviews, (1993), 93, 847-880,for example the discussion of superstructures on polydentate ligands atpages 856-857, and references cited therein, as well as B. K. Coltrainet al., “Oxygen Activation by Transition Metal Complexes ofMacrobicyclic Cyclidene Ligands” in “The Activation of Dioxygen andHomogeneous Catalytic Oxidation”, Ed. by E. H. R. Barton, et al. (PlenumPress, NY; 1993), pp. 359-380.

More recently the literature on azamacrocycles has grown at a rapidpace. Among the many references are Hancock et. al., J. Chem. Soc.,Chem. Commun., (1987), 1129-1130; Weisman et al., “Synthesis andTransition Metal Complexes of New Cross-Bridged Tetraamine Ligands”,Chem. Commun., (1996), 947-948; U.S. Pat. No. 5,428,180, U.S. Pat. No.5,504,075, and U.S. Pat. No. 5,126,464, all to Burrows et al.; U.S. Pat.No. 5,480,990, to Kiefer et al.; and U.S. Pat. No. 5,374,416, toRousseaux et al.

Homogeneous transition metal catalysis is a broad realm that has enjoyedintensive activity leading to a number of large scale chemicalprocesses; e.g., the Monsanto acetic acid process, the Dupontadiponitrile process, and others, among which certain famous onesinvolve oxidations (Wacker Process, Midcentury Process). Further,transition metal oxidation catalysis has been promoted heavily instudies on the biomimicry of the monooxygenase enzymes, especiallycytochrome P450. Whereas such studies have emphasized and shown theprowess of the native porphyrin prosthetic group, others have shown thatcertain oxidative capabilities exist in the same metal ions in thesimple solvated condition. This history reveals the possibility thatcatalytic oxidation may alter almost all families of organic compoundsto yield valuable products, but successful applications depend on theactivity of the putative catalyst, it survivability under reactionconditions, its selectivity, and the absence of undesirable sidereactions or over-reaction.

It has now surprisingly been determined that the use of certaintransition-metal catalysts of specific rigid macropolycycles, preferablycontaining cross-bridging, have exceptional kinetic stability such thatthe metal ions only dissociate very slowly under conditions which woulddestroy complexes with ordinary ligands, and further have exceptionalthermal stability. Thus, the present invention catalyst systems canprovide one or more important benefits. These include improvedeffectiveness and in some instances even synergy with one or moreprimary oxidants such as hydrogen peroxide, hydrophilically orhydrophobically activated hydrogen peroxide, preformed peracids,monopersulfate or hypochlorite; the ability to be effective catalysts,some, especially those containing Mn(II), having little to no color andallowing great formulation flexibility for use in consumer productswhere product aesthetics are very important; and effectiveness on avariety of substrates and reactants, including a variety of soiled orstained fabrics or hard surfaces while minimizing tendency to stain ordamage such surfaces.

Therefore, the present invention provides improved catalytic systemscontaining transition-metal oxidation catalysts, and methods whichutilize these catalysts and catalytic systems in the area of chemicalsyntheses involving organic oxidation reactions, such as oxidation oforganic functional groups, hydrocarbons, or heteroatoms, and epoxidationof alkenes; oxidation of oxidizable stains on fabrics and hard surfaces;oxidation of reactants in solutions; pulp and paper bleaching; theoxidation of organic pollutants and for other equivalent highlydesirable purposes.

These and other objects are secured herein, as will be seen from thefollowing disclosures.

BACKGROUND ART

Transition metals such as manganese are well-known in oxidation systems.Free Mn⁺² ions have, for example, been implicated in the oxidation oflignin by white rot mycetes. Manganese and other transition metals incomplexed form are familiar in biological systems with a variety ofligands. See, for example, “The Biological Chemistry of the Elements”,J. J. R. Fraustro da Silva and R. J. P. Williams, Clarendon Press,Oxford, reprinted 1993. Complexes of ligands such as substitutedporphyrins with iron, manganese, chromium or ruthenium are asserted tobe useful in catalyzing a variety of oxidative reactions, includingoxidation of lignin and industrial pollutants. See, for example, U.S.Pat. No. 5,077,394.

A recent review of nickel-catalyzed oxidations includes the followingdisclosures: (1) simple tetradentate ligands such as cyclam (anon-cross-bridged, N—H functional tetraazamacrocycle) or salen (afour-donor N,N,O,O ligand) render Ni(II) active for olefin epoxidation;(2) Ni salen complexes can utilize sodium hypochlorite as primaryoxidant and show high catalytic turnover in epoxidation reactions; (3)bleach can be used under phase-transfer conditions for manganeseporphyrin-catalyzed epoxidations and can be adapted to Ni as well; and(4) reactivity is dramatically influenced by pH with conversion ofstyrenes into epoxides being quantitative under conditions said to beoptimized at pH 9.3.

The catalysis of oxidation reactions by transition metals is moregenerally useful in synthetic organic chemistry in such varied aspectsof the chemical process industry as commodity chemical production anddrug manufacture, in addition to the laboratory, and also in consumerproduct applications such as detergency. Laundry bleaching in general isreviewed in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd and4th editions under a number of headings including “Bleaching Agents”,“Detergents” and “Peroxy Compounds”. Laundry applications of bleachingsystems include the use of amido-derived bleach activators in laundrydetergents as described in U.S. Pat. No. 4,634,551. The use of manganesewith various ligands to enhance bleaching is reported in the followingUnited States Patents: U.S. Pat. No. 4,430,243; U.S. Pat. No. 4,728,455;U.S. Pat. No. 5,246,621; U.S. Pat. No. 5,244,594; U.S. Pat. No.5,284,944; U.S. Pat. No. 5,194,416; U.S. Pat. No. 5,246,612; U.S. Pat.No. 5,256,779; U.S. Pat. No. 5,280,117; U.S. Pat. No. 5,274,147; U.S.Pat. No. 5,153,161; U.S. Pat. No. 5,227,084; U.S. Pat. No. 5,114,606;U.S. Pat. No. 5,114,611. See also: EP 549,271 A1; EP 544,490 A1; EP549,272 A1; and EP 544,440 A2.

U.S. Pat. No. 5,580,485 describes a bleach and oxidation catalystcomprising an iron complex having formula A[LFeX_(n)]^(Z)Y_(q)(A) orprecursors thereof. The most preferred ligand is said to beN,N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine, N₄Py. TheFe-complex catalyst is said to be useful in a bleaching systemcomprising a peroxy compound or a precursor thereof and suitable for usein the washing and bleaching of substrates including laundry,dishwashing and hard surface cleaning. Alternatively, the Fe-complexcatalyst is assertedly also useful in the textile, paper and wood-pulpindustries.

The art of the transition metal chemistry of macrocycles is enormous;see, for example “Heterocyclic compounds: Aza-crown macrocycles”, J. S.Bradshaw et. al., Wiley-Interscience, 1993 which also describes a numberof syntheses of such ligands. See especially the table beginning at p.604. U.S. Pat. No. 4,888,032 describes salts of cationic metal dry cavecomplexes.

Cross-bridging, i.e., bridging across nonadjacent nitrogens, of cyclam(1,4,8,11-tetraazacyclotetradecane) is described by Weisman et al, J.Amer. Chem. Soc., (1990), 112(23), 8604-8605. More particularly, Weismanet al., Chem. Commun., (1996), pp. 947-948 describe new cross-bridgedtetraamine ligands which are bicyclo[6.6.2], [6.5.2], and [5.5.2]systems, and their complexation to Cu(II) and Ni(II) demonstrating thatthe ligands coordinate the metals in a cleft. Specific complexesreported include those of the ligands 1.1:

in which A is hydrogen or benzyl and (a) m=n=1; or (b) m=1 and n=0; or(c) m=n=0, including a Cu(II)chloride complex of the ligand having A=Hand m=n=1; Cu(II) perchlorate complexes where A=H and m=n=1 or m=n=0; aCu(II)chloride complex of the ligand having A=benzyl and m=n=0; and aNi(II)bromide complex of the ligand having A=H and m=n=1. In someinstances halide in these complexes is a ligand, and in other instancesit is present as an anion. This handful of complexes appears to be thetotal of those known wherein the cross-bridging is not across “adjacent”nitrogens.

Ramasubbu and Wainwright, J. Chem. Soc., Chem. Commun., (1982), 277-278in contrast describe structurally reinforcing cyclen by bridgingadjacent nitrogen donors. Ni(II) forms a pale yellow mononucleardiperchlorate complex having one mole of the ligand in a square planarconfiguration. Kojima et al, Chemistry Letters, (1996), pp. 153-154,describes assertedly novel optically active dinuclear Cu(II) complexesof a structurally reinforced tricyclic macrocycle.

Bridging alkylation of saturated polyaza macrocycles as a means forimparting structural rigidity is described by Wainwright, Inorg. Chem.,(1980), 19(5), 1396-8. Mali, Wade and Hancock describe a cobalt (III)complex of a structurally reinforced macrocycle, see J. Chem. Soc.,Dalton Trans., (1992), (1), 67-71. Seki et al describe the synthesis andstructure of chiral dinuclear copper(II) complexes of an assertedlynovel reinforced hexaazamacrocyclic ligand; see Mol. Cryst. Liq. Cryst.Sci. Technol., Sect. A (1996), 276, 79-84; see also related work by thesame authors in the same Journal at 276, 85-90 and 278, 235-240.

[Mn(III)₂(μ-O)(μ-O₂CMe)₂L₂]²⁺ and [Mn(IV)₂(μ-O)₃L₂]²⁺ complexes derivedfrom a series of N-substituted 1,4,7-triazacyclononanes are described byKoek et al., see J. Chem. Soc., Dalton Trans., (1996), 353-362.Important earlier work by Wieghardt and co-workers on1,4,7-triazacyclononane transition metal complexes, including those ofManganese, is described in Angew. Chem. Internat. Ed. Engl., (1986), 25,1030-1031 and J. Amer. Chem. Soc., (1988), 110, 7398.

Ciampolini et al., J. Chem. Soc., Dalton Trans., (1984), 1357-1362describe synthesis and characterization of the macrocycle1,7-dimethyl-1,4,7,10-tetraazacyclododecane and of certain of its Cu(II)and Ni(II) complexes including both a square-planar Ni complex and acis-octahedral complex with the macrocycle co-ordinated in a foldedconfiguration to four sites around the central nickel atom. Hancock etal, Inorg. Chem., (1990), 29, 1968-1974 describe ligand designapproaches for complexation in aqueous solution, including chelate ringsize as a basis for control of size-based selectivity for metal ions.Thermodynamic data for macrocycle interaction with cations, anions andneutral molecules is reviewed by Izatt et al., Chem. Rev., (1995), 95,2529-2586 (478 references).

Bryan et al, Inorg. Chem., (1975), 14(2)., 296-299 describe synthesisand characterization of Mn(II) and Mn(III) complexes ofmeso-5,5,7-12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane([14]aneN4]. The isolated solids are assertedly frequently contaminatedwith free ligand or “excess metal salt” and attempts to prepare chlorideand bromide derivatives gave solids of variable composition which couldnot be purified by repeated crystallization.

Costa and Delgado, Inorg. Chem., (1993), 32, 5257-5265, describe metalcomplexes such as the Co(II), Ni(II) and Cu(II) complexes, ofmacrocyclic complexes containing pyridine. Derivatives of thecross-bridged cyclens, such as salts of4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane, are describedby Bencini et al., see Supramolecular Chemistry, 3, 141-146. U.S. Pat.No. 5,428,180 and related work by Cynthia Burrows and co-workers in U.S.Pat. No. 5,272,056 and U.S. Pat. No. 5,504,075 describe pH dependence ofoxidations using cyclam or its derivatives, oxidations of alkenes toepoxides using metal complexes of such derivatives, and pharmaceuticalapplications. Hancock et al., Inorganica Chimica Acta., (1989), 164,73-84 describe under a title including “complexes of structurallyreinforced tetraaza-macrocyclic ligands of high ligand field strength”the synthesis of complexes of low-spin Ni(II) with three assertedlynovel bicyclic macrocycles. The complexes apparently involve nearlycoplanar arrangements of the four donor atoms and the metals despite thepresence of the bicyclic ligand arrangement. Bencini et al., J. Chem.Soc., Chem. Commun., (1990), 174-175 describe synthesis of a smallaza-cage, 4,10-dimethyl- 1,4,7,10-15-pentaazabicyclo[5.5.5]heptadecane,which “encapsulates” lithium. Hancock and Martell, Chem. Rev., (1989),89, 1875-1914 review ligand design for selective complexation of metalions in aqueous solution. Conformers of cyclam complexes are discussedon page 1894 including a folded conformer—see FIG. 18 (cis-V). The paperincludes a glossary. In a paper entitled “Structurally ReinforcedMacrocyclic Ligands that Show Greatly Enhanced Selectivity for MetalIons on the Basis of the Match and Size Between the Metal Ion and theMacrocyclic Cavity”, Hancock et al., J. Chem. Soc., Chem. Commun.,(1987), 1129-1130 describe formation constants for Cu(II), Ni(II) andother metal complexes of some bridged macrocycles having piperazine-likestructure.

Many other macrocycles are described in the art, including types withpedant groups and a wide range of intracyclic and exocyclicsubstituents. Although the macrocycle and transition metal complexliterature are, separately, vast, relatively little appears to have beenreported on how to select and combine specific transition metals andspecific macrocycle classes, for example cross-bridged tetraaza- andpenta-aza macrocycles, so as to apply them for the further improvementof oxidation catalysis. There is, for example, no apparent singling outof these materials from the vast chemical literature, either alone or astheir transition metal complexes, for use in bleaching detergents.

SUMMARY OF THE INVENTION

The present invention relates to a method for oxidizing materials, saidmethod comprising contacting (preferably in the presence of a solvent,such as water, non-aqueous solvents, and mixtures thereof) a materialcapable of being oxidized with an oxidation agent and a transition-metaloxidation catalyst, wherein said transition-metal oxidation catalystcomprises a complex of a transition metal selected from the groupconsisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV),Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III),Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV),Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV),preferably Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III), Fe(IV), Cr(II),Cr(II), Cr(IV), Cr(V), and Cr(VI), preferably Mn, Fe and Cr in the (II)or (III) state, coordinated with a macropolycyclic rigid ligand,preferably a cross-bridged macropolycyclic ligand, having at least 3donor atoms, at least two of which are bridgehead donor atoms.

The present invention also relates to catalytic systems effective foroxidation of materials comprising: (a) a catalytically effective amount,preferably from about 1 ppb to about 99.9%, more typically from about0.001 ppm to about 500 ppm, preferably from about 0.05 ppm to about 100ppm (wherein “ppb” denotes parts per billion by weight and “ppm” denotesparts per million by weight), of a transition-metal oxidation catalyst,wherein said transition-metal oxidation catalyst comprises a complex ofa transition metal selected from the group consisting of Mn(II),Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III),Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV),Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V),W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV) coordinated with amacropolycyclic rigid ligand, preferably a cross-bridged macropolycyclicligand, having at least 3 donor atoms, at least two of which arebridgehead donor atoms; and (b) the balance, to 100%, of one or moreadjunct materials.

Amounts of the essential transition-metal catalyst and essential adjunctmaterials can vary widely depending on the precise application. Forexample, the catalytic systems herein may be provided as a concentrate,in which case the catalyst can be present in a high proportion, forexample 0.01% -80%, or more, of the composition. The invention alsoencompasses catalytic systems at their in-use levels; such systemsinclude those in which the catalyst is dilute, for example at ppblevels. Intermediate level compositions, for example those comprisingfrom about 0.01 ppm to about 500 ppm, more preferably from about 0.05ppm to about 50 ppm, more preferably still from about 0.1 ppm to about10 ppm of transition-metal catalyst and the balance to 100%, preferablyat least about 0.1%, typically about 99% or more being solid-form orliquid-form adjunct materials (for example fillers, solvents, andadjuncts especially adapted to a particular use (for example papermakingadjuncts, detergent adjuncts, or the like). The invention alsoencompasses a large number of novel transition-metal catalysts per-se,especially including their substantially pure (100% active) forms.

The present invention preferably relates to catalytic systems effectivefor oxidation of materials comprising: (a) a catalytically effectiveamount, preferably from about 1 ppb to about 49%, of a transition-metaloxidation catalyst, said catalyst comprising a complex of a transitionmetal and a macropolycyclic rigid ligand, preferably a cross-bridgedmacropolycyclic ligand, wherein:

(1) said transition metal is selected from the group consisting ofMn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II),Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II),Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V),Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV);

(2) said macropolycyclic rigid ligand is coordinated by at least three,preferably at least four, more preferably four or five, donor atoms tothe same transition metal and comprises:

(i) an organic macrocycle ring containing three, preferably four, ormore donor atoms (preferably at least 3, more preferably at least 4, ofthese donor atoms are N) separated from each other by covalent linkagesof at least one, preferably 2 or 3, non-donor atoms, two to five(preferably three to four, more preferably four) of these donor atomsbeing coordinated to the same transition metal in the complex;

(ii) a linking moiety, preferably a cross-bridging chain, whichcovalently connects at least 2 (preferably non-adjacent) donor atoms ofthe organic macrocycle ring, said covalently connected (preferablynon-adjacent) donor atoms being bridgehead donor atoms which arecoordinated to the same transition metal in the complex, and whereinsaid linking moiety (preferably a cross-bridged chain) comprises from 2to about 10 atoms (preferably the cross-bridged chain is selected from2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a further donoratom), including for example, a cross-bridge which is the result of aMannich condensation of ammonia and formaldehyde; and (

iii) optionally, one or more non-macropolycyclic ligands, preferablymonodentate ligands, such as those selected from the group consisting ofH₂O, ROH, NR₃, RCN, OH⁻, OOH⁻, RS⁻, RO⁻, RCOO⁻, OCN⁻, SCN⁻, N₃ ⁻, CN⁻,F⁻, Cl⁻, Br⁻, I⁻, O₂ ⁻, NO₃ ⁻, NO₂ ⁻, SO₄ ²⁻, SO₃ ²⁻, PO₄ ³⁻, organicphosphates, organic phosphonates, organic sulfates, organic sulfonates,and aromatic N donors such as pyridines, pyrazines, pyrazoles,imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles with Rbeing H, optionally substituted alkyl, optionally substituted aryl(specific examples of monodentate ligands including phenolate, acetateor the like); and

(b) at least about 0.1%, preferably B %, of one or more adjunctmaterials (where B %, the “balance” of the composition expressed as apercentage, is obtained by subtracting the weight of said component (a)from the weight of the total composition and then expressing the resultas a percentage by weight of the total composition).

The present invention also preferably relates to catalytic systemseffective for oxidation of materials comprising: (a) a catalyticallyeffective amount, as identified supra, of a transition-metal oxidationcatalyst, said catalyst comprising a complex of a transition metal and amacropolycyclic rigid ligand (preferably a cross-bridged macropolycyclicligand) wherein: (1) said transition metal is selected from the groupconsisting of Mn(II), Mn(II), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV),Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III),Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV),Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(II), and Ru(IV),and (2) said macropolycyclic rigid ligand is selected from the groupconsisting of: (i) the macropolycyclic rigid ligand of formula (I)having denticity of 3 or 4:

(ii) the macropolycyclic rigid ligand of formula (II) having denticityof 4 or 5:

(iii) the macropolycyclic rigid ligand of formula (III) having denticityof 5 or 6:

(iv) the macropolycyclic rigid ligand of formula (IV) having denticityof 6 or 7:

wherein in these formulas:

each “E” is the moiety (CR_(n))_(a)-X-(CR_(n))_(a′), wherein X isselected from the group consisting of O, S, NR and P, or a covalentbond, and preferably X is a covalent bond and for each E the sum of a+a′is independently selected from 1 to 5, more preferably 2 and 3;

each “G” is the moiety (CR_(n))_(b);

each “R” is independently selected from H, alkyl, alkenyl, alkynyl,aryl, alkylaryl (e.g., benzyl), and heteroaryl, or two or more R arecovalently bonded to form an aromatic, heteroaromatic, cycloalkyl, orheterocycloalkyl ring;

each “D” is a donor atom independently selected from the groupconsisting of N, O, S, and P, and at least two D atoms are bridgeheaddonor atoms coordinated to the transition metal (in the preferredembodiments, all donor atoms designated D are donor atoms whichcoordinate to the transition metal, in contrast with heteroatoms in thestructure which are not in D such as those which may be present in E;the non-D heteroatoms can be non-coordinating and indeed arenon-coordinating whenever present in the preferred embodiment);

“B” is a carbon atom or “D” donor atom, or a cycloalkyl or heterocyclicring;

each “n” is an integer independently selected from 1 and 2, completingthe valence of the carbon atoms to which the R moieties are covalentlybonded;

each “n”′ is an integer independently selected from 0 and 1, completingthe valence of the D donor atoms to which the R moieties are covalentlybonded;

each “n”″ is an integer independently selected from 0, 1, and 2completing the valence of the B atoms to which the R moieties arecovalently bonded;

each “a” and “a”′ is an integer independently selected from 0-5,preferably a+a′ equals 2 or 3, wherein the sum of all “a” plus “a”′ inthe ligand of formula (I) is within the range of from about 7 to about12, the sum of all “a” plus “a”′ in the ligand of formula (II) is withinthe range of from about 6 (preferably 8) to about 12, the sum of all “a”plus “a”′ in the ligand of formula (III) is within the range of fromabout 8 (preferably 10) to about 15, and the sum of all “a” plus “a”′ inthe ligand of formula (IV) is within the range of from about 10(preferably 12) to about 18;

each “b” is an integer independently selected from 0-9, preferably 0-5(wherein when b=0, (CR_(n))₀ represents a covalent bond), or in any ofthe above formulas, one or more of the (CR_(n))_(b) moieties covalentlybonded from any D to the B atom is absent as long as at least two(CR_(n))_(b) covalently bond two of the D donor atoms to the B atom inthe formula, and the sum of all “b” is within the range of from about 1to about 5; and

(iii) optionally, one or more non-macropolycyclic ligands; and

(b) adjunct materials at suitable levels, as identified hereinabove.

The present invention also includes many novel transition-metalcomplexes which are useful oxidation catalysts. Such transition-metalcomplexes include: Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III),Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II),Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V),Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), andRu(IV), preferably Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III), Cr(II),Cr(III), Cr(IV), Cr(V), and Cr(VI), more preferably the Mn(II), Mn(III),Mn(IV), Mn(V), Fe(II), Fe(III), Fe (IV), Cr(II) and Cr(III) complexes ofthe cross-bridged tetraazamacrocycles and cross-bridgedpentaazamacrocycles; these complexes include those in which thecross-bridging moiety is a C2-C4 alkyl moiety and in which there is amole ratio of macrocycle to metal of 1:1, and moreover these are mostpreferably monometallic mononuclear complexes, though in general,dimetallic or multimetallic complexes are not excluded.

To further illustrate, a preferred sub-group of the inventivetransition-metal complexes includes the Mn(II), Fe(II) and Cr(III)complexes of the ligand 1.2:

wherein m and n are integers from 0 to 2, p is an integer from 1 to 6,preferably m and n are both 0 or both 1 (preferably both 1), or m is 0and n is at least 1; and p is 1; and A is a nonhydrogen moietypreferably having no aromatic content; more particularly each A can varyindependently and is preferably selected from methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, C5-C20 alkyl, and one, but notboth, of the A moieties is benzyl, and combinations thereof. In one suchcomplex, one A is methyl and one A is benzyl.

All parts, percentages and ratios used herein are expressed as percentweight unless otherwise specified. All documents cited are, in relevantpart, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

Catalytic Systems for Oxidizing Materials:

The catalytic systems of the present invention comprise a particularlyselected transition-metal oxidation catalyst which is a complex of atransition metal and a macropolycyclic rigid ligand, preferably onewhich is cross-bridged; the catalytic systems preferably also comprisean oxidation agent or “primary oxidant”, preferably one which is a lowcost, readily available substance producing little or no waste, such asa source of hydrogen peroxide. The source of hydrogen peroxide can beH₂O₂ itself, its solutions, or any common hydrogen-peroxide releasingsalt, adduct or precursor, such as sodium perborate, sodiumpercarbonate, or mixtures thereof. Also useful are other sources ofavailable oxygen such as persulfate (e.g., OXONE, manufactured byDuPont), as well as preformed organic peracids and other organicperoxides. More generally, chlorine or other oxidants such as ClO₂ orNaOCl can be used.

Mixtures of primary oxidants can be used; in such mixtures, an oxidantwhich is not present in major proportion can be used, for example as inmixtures of a major proportion of hydrogen peroxide and a minorproportion of peracetic acid or its salts. In this example, theperacetic acid is termed the “secondary oxidant”. Secondary oxidants canbe selected from the same list of oxidants given hereinafter; the use ofsecondary oxidants is optional but may be highly desirable in certainembodiments of the invention. The catalytic system often furthercomprises further adjuncts, including compounds which liberate oxidantas a result of in-situ chemical reaction; as well as solvents and otheradditives characteristic of the end-use of the catalytic system. Tosecure the benefits of the invention, a substrate material, such as achemical compound to be oxidized, or a commercial mixture of materialssuch as a paper pulp, or a soiled material such as a textile containingone or more materials or soils to be oxidized, is added to the catalyticsystem under widely ranging conditions further described hereinafter.

The catalytic systems herein are useful for oxidative syntheticchemistry processes, such as oxidation of organic functional groups,hydrocarbons, heteroatoms, and epoxidation (including enantiomeric) ofalkenes and enynes, oxidation of sulfides to sulfones, and the like.

The present invention catalytic systems also have utility in the area ofoxidizing (preferably including bleaching) wood pulp for use in, forexample, paper making processes. Other utilities include oxidativedestruction of waste materials or effluents.

Effective Amounts of Catalyst Materials

The term “catalytically effective amount”, as used herein, refers to anamount of the transition-metal oxidation catalyst present in the presentinvention catalytic systems, or during use according to the presentinvention methods, that is sufficient, under whatever comparative or useconditions are employed, to result in at least partial oxidation of thematerial sought to be oxidized by the catalytic systems or method. Forexample, in the synthesis of epoxides from alkenes, the catalytic amountis that amount which is sufficient to catalyze the desired epoxidationreaction. As noted, the invention encompasses catalytic systems both attheir in-use levels and at the levels which may commercially be providedfor sale as “concentrates”; thus “catalytic systems” herein include boththose in which the catalyst is highly dilute and ready to use, forexample at ppb levels, and compositions having rather higherconcentrations of catalyst and adjunct materials. Intermediate levelcompositions, as noted in summary, can include those comprising fromabout 0.01 ppm to about 500 ppm, more preferably from about 0.05 ppm toabout 50 ppm, more preferably still from about 0.1 ppm to about 10 ppmof transition-metal catalyst and the balance to 100%, typically about99% or more, being solid-form or liquid-form adjunct materials (forexample fillers, solvents, and adjuncts especially adapted to aparticular use, such as papermaking adjuncts, detergent adjuncts, or thelike). In terms of amounts of materials, the invention also encompassesa large number of novel transition-metal catalysts per-se, especiallyincluding their substantially pure (100% active) forms. Other amounts,for example of oxidant materials and other adjuncts for specializeduses, are illustrated in more detail hereinafter.

Transition-Metal Oxidation Catalysts:

The present invention catalytic systems comprise a transition-metaloxidation catalyst. In general, the catalyst contains an at leastpartially covalently bonded transition metal, and bonded thereto atleast one particularly defined macropolycyclic rigid ligand, preferablyone having four or more donor atoms and which is cross-bridged orotherwise tied so that the primary macrocycle ring complexes in a foldedconformation about the metal. Catalysts herein are thus neither of themore conventional macrocyclic type: e.g., porphyrin complexes, in whichthe metal can readily adopt square-planar configuration; nor are theycomplexes in which the metal is fully encrypted in a ligand. Rather, thepresently useful catalysts represent a selection of all the manycomplexes, hitherto largely unrecognized, which have an intermediatestate in which the metal is bound in a “cleft”. Further, there can bepresent in the catalyst one or more additional ligands, of generallyconventional type such as chloride covalently bound to the metal; and,if needed, one or more counter-ions, most commonly anions such aschloride, hexafluorophosphate, perchlorate or the like; and additionalmolecules to complete crystal formation as needed, such as water ofcrystallization. Only the transition-metal and macropolycyclic rigidligand are, in general, essential.

Transition-metal oxidation catalysts useful in the invention catalyticsystems can in general include known compounds where they conform withthe invention definition, as well as, more preferably, any of a largenumber of novel compounds expressly designed for the present oxidationcatalysis uses and non-limitingly illustrated by any of the following:

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II)

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2] hexadecaneManganese(II) Hexafluorophosphate

Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Hexafluorophosphate

Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II) Hexafluorophosphate

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Tetrafluoroborate

Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II) Tetrafluoroborate

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Hexafluorophosphate

Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza- bicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza- bicyclo[6.6.2]hexadecane Manganese(II)

Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza- bicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza- bicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneIron(II)

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneIron(II)

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneCopper(II)

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneCopper(II)

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneCobalt(II)

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneCobalt(II)

Dichloro5,12-dimethyl--4-phenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese (II)

Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese (II)

Dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II)

Dichloro-2,4,5,9,11,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese (II)

Dichloro-2,2,4,5,9,11,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese (II)

Dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese (II)

Dichloro-3,5,10,12-tetramethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)

Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)

Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Iron(II)

Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Iron(II)

Aquo-chloro-2-(2-hydroxyphenyl)-5,12-dimethyl,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Aquo-chloro-10-(2-hydroxybenzyl)-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)

Chloro-2-(2-hydroxybenzyl)-5-methyl,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Chloro-10-(2-hydroxybenzyl)-4-methyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II)

Chloro-5-methyl-12-(2-picolyl)-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Chloride

Chloro-4-methyl-10-(2-picolyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II) Chloride

Dichloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III)

Aquo-Chloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Aquo-Chloro-5-(3-sulfonopropyl)-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)

Dichloro-5-(Trimethylammoniopropyl)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Chloride

Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo[8.5.2]heptadecaneManganese(II)

Dichloro-14,20-dimethyl-1,10,14,20-tetraazatriyclo[8.6.6]docosa-3(8),4,6-trieneManganese(II)

Dichloro-4,11-dimethyl-1,4,7,11-tetraazabicyclo[6.5.2]pentadecaneManganese(II)

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[7.6.2]heptadecaneManganese(II)

Dichloro-5,13-dimethyl-1,5,9,13-tetraazabicyclo[7.7.2]heptadecaneManganese(II)

Dichloro-3,10-bis(butylcarboxy)-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Diaquo-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Chloro-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaenemanganese(II) Hexafluorophosphate

Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaene Manganese(II) Trifluoromethanesulfonate

Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaeneIron(II) Trifluoromethanesulfonate

Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecaneManganese(II) Hexafluorophosphate

Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5] heptadecaneManganese(II) Hexafluorophosphate

Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecaneManganese(II) Chloride

Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecaneManganese(II) Chloride

Preferred complexes useful as transition-metal oxidation catalysts moregenerally include not only monometallic, mononuclear kinds such as thoseillustrated hereinabove but also bimetallic, trimetallic or clusterkinds, especially when the polymetallic kinds transform chemically inthe presence of a primary oxidant to form a mononuclear, monometallicactive species. Monometallic, mononuclear complexes are preferred. Asdefined herein, a monometallic transition-metal oxidation catalystcontains only one transition metal atom per mole of complex. Amonometallic, mononuclear complex is one in which any donor atoms of theessential macrocyclic ligand are bonded to the same transition metalatom, that is, the essential ligand does not “bridge” across two or moretransition-metal atoms.

Transition Metals of the Catalyst

Just as the macropolycyclic ligand cannot vary indeterminately for thepresent useful purposes, nor can the metal. An important part of theinvention is to arrive at a match between ligand selection and metalselection which results in excellent oxidation catalysis. In general,transition-metal oxidation catalysts herein comprise a transition metalselected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V),Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III),Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III),V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II),Ru(III), and Ru(IV).

Preferred transition-metals in the instant transition-metal oxidationcatalyst include manganese, iron and chromium. Preferred oxidationstates include the (II) and (III) oxidation states. Manganese(II) inboth the low-spin configuration and high spin complexes are included. Itis to be noted that complexes such as low-spin Mn(II) complexes arerather rare in all of coordination chemistry. The designation (II) or(III) denotes a coordinated transition metal having the requisiteoxidation state; the coordinated metal atom is not a free ion or onehaving only water as a ligand.

Ligands

In general, as used herein, a “ligand” is any moiety capable of directcovalent bonding to a metal ion. Ligands can be charged or neutral andmay range widely, including simple monovalent donors, such as chloride,or simple amines which form a single coordinate bond and a single pointof attachment to a metal; to oxygen or ethylene, which can form athree-membered ring with a metal and thus can be said to have twopotential points of attachment, to larger moieties such asethylenediamine or aza macrocycles, which form up to the maximum numberof single bonds to one or more metals that are allowed by the availablesites on the metal and the number of lone pairs or alternate bondingsites of the free ligand. Numerous ligands can form bonds other thansimple donor bonds, and can have multiple points of attachment.

Ligands useful herein can fall into several groups: the essentialmacropolycyclic rigid ligand, preferably a cross-bridged macropolycycle(preferably there will be one such ligand in a useful transition-metalcomplex, but more, for example two, can be present, but not in preferredmononuclear complexes); other, optional ligands, which in general aredifferent from the essential cross-bridged macropolycycle (generallythere will be from 0 to 4, preferably from 1 to 3 such ligands); andligands associated transiently with the metal as part of the catalyticcycle, these latter typically being related to water, hydroxide, oxygen,water, hydroxide, or peroxides. Ligands of the third group are notessential for defining the metal oxidation catalyst, which is a stable,isolable chemical compound that can be fully characterized. Ligandswhich bind to metals through donor atoms each having at least a singlelone pair of electrons available for donation to a metal have a donorcapability, or potential denticity, at least equal to the number ofdonor atoms. In general, that donor capability may be fully or onlypartially exercised.

Macropolycyclic Rigid Ligands

To arrive at the instant transition-metal catalysts, a macropolycyclicrigid ligand is essential. This is coordinated (covalently connected toany of the above-identified transition-metals) by at least three,preferably at least four, and most preferably four or five, donor atomsto the same transition metal.

Generally, the macropolycyclic rigid ligands herein can be viewed as theresult of imposing additional structural rigidity on specificallyselected “parent macrocycles”. The term “rigid” herein has been definedas the constrained converse of flexibility: see D. H. Busch., ChemicalReviews., (1993), 93, 847-860, incorporated by reference. Moreparticularly, “rigid” as used herein means that the essential ligand, tobe suitable for the purposes of the invention, must be determinably morerigid than a macrocycle (“parent macrocycle”) which is otherwiseidentical (having the same ring size and type and number of atoms in themain ring) but lacks the superstructure (especially linking moieties or,preferably cross-bridging moieties) of the present ligands. Indetermining the comparative rigidity of the macrocycles with and withoutsuperstructures, the practitioner will use the free form (not themetal-bound form) of the macrocycles. Rigidity is well-known to beuseful in comparing macrocycles; suitable tools for determining,measuring or comparing rigidity include computational methods (see, forexample, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancocket al., Inorganica Chimica Acta, (1989), 164, 73-84. A determination ofwhether one macrocycle is more rigid than another can be often made bysimply making a molecular model, thus it is not in general essential toknow configurational energies in absolute terms or to precisely computethem. Excellent comparative determinations of rigidity of one macrocyclevs. another can be made using inexpensive personal computer-basedcomputational tools, such as ALCHEMY III, commercially available fromTripos Associates. Tripos also has available more expensive softwarepermitting not only comparative, but absolute determinations;alternately, SHAPES can be used (see Zimmer cited supra). Oneobservation which is significant in the context of the present inventionis that there is an optimum for the present purposes when the parentmacrocycle is distinctly flexible as compared to the cross-bridged form.Thus, unexpectedly, it is preferred to use parent macrocycles containingat least four donor atoms, such as cyclam derivatives, and tocross-bridge them, rather than to start with a more rigid parentmacrocycle. Another observation is that cross-bridged macrocycles aresignificantly preferred over macrocycles which are bridged in othermanners.

The macrocyclic rigid ligands herein are of course not limited to beingsynthesized from any preformed macrocycle plus preformed “rigidizing” or“conformation-modifying” element: rather, a wide variety of syntheticmeans, such as template syntheses, are useful. See for example Busch etal., reviewed in “Heterocyclic compounds: Aza-crown macrocycles”, J. S.Bradshaw et. al., referred to in the Background Section hereinbefore,for synthetic methods.

In one aspect of the present invention, the macropolycyclic rigidligands herein include those comprising:

(i) an organic macrocycle ring containing three, preferably four, ormore donor atoms (preferably at least 3, more preferably at least 4, ofthese donor atoms are N) separated from each other by covalent linkagesof at least one, preferably 2 or 3, non-donor atoms, two to five(preferably three to four, more preferably four) of these donor atomsbeing coordinated to the same transition metal in the complex; and

(ii) a linking moiety, preferably a cross-bridging chain, whichcovalently connects at least 2 (preferably non-adjacent) donor atoms ofthe organic macrocycle ring, said covalently connected (preferablynon-adjacent) donor atoms being bridgehead donor atoms which arecoordinated to the same transition metal in the complex, and whereinsaid linking moiety (preferably a cross-bridged chain) comprises from 2to about 10 atoms (preferably the cross-bridged chain is selected from2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a further donoratom).

While clear from the various contexts and illustrations alreadypresented, the practitioner may further benefit if certain terms receiveadditional definition and illustration. As used herein, “macrocyclicrings” are covalently connected rings formed from three or more,preferably four or more, donor atoms (i.e., heteroatoms such as nitrogenor oxygen) with carbon chains connecting them, and any macrocycle ringas defined herein must contain a total of at least ten, preferably atleast twelve, atoms in the macrocycle ring. A macropolycyclic rigidligand herein may contain more than one ring of any sort per ligand, butat least one macrocycle ring must be identifiable. Moreover, in thepreferred embodiments, no two hetero-atoms are directly connected.Preferred transition-metal oxidation catalysts are those wherein themacropolycyclic rigid ligand comprises an organic macrocycle ring (mainring) containing at least 10-20 atoms, preferably 12-18 atoms, morepreferably from about 12 to about 20 atoms, most preferably 12 to 16atoms.

“Donor atoms” herein are heteroatoms such as nitrogen, oxygen,phosphorus or sulfur, which when incorporated into a ligand still haveat least one lone pair of electrons available for forming adonor-acceptor bond with a metal. Preferred transition-metal oxidationcatalyst are those wherein the donor atoms in the organic macrocyclering of the cross-bridged macropolycyclic ligand are selected from thegroup consisting of N, O, S, and P, preferably N and O, and mostpreferably all N. Also preferred are cross-bridged macropolycyclicligands comprising 4 or 5 donor atoms, all of which are coordinated tothe same transition metal. Most preferred transition-metal oxidationcatalysts are those wherein the cross-bridged macropolycyclic ligandcomprises 4 nitrogen donor atoms all coordinated to the same transitionmetal, and those wherein the cross-bridged macropolycyclic ligandcomprises 5 nitrogen atoms all coordinated to the same transition metal.

“Non-donor atoms” of the macropolycyclic rigid ligand herein are mostcommonly carbon, though a number of atom types can be included,especially in optional exocyclic substituents (such as “pendant”moieties, illustrated hereinafter) of the macrocycles, which are neitherdonor atoms for purposes essential to form the metal catalysts, nor arethey carbon. Thus, in the broadest sense, the term “non-donor atoms” canrefer to any atom not essential to forming donor bonds with the metal ofthe catalyst. Examples of such atoms could include heteroatoms such assulfur as incorporated in a non-coordinatable sulfonate group,phosphorus as incorporated into a phosphonium salt moiety, phosphorus asincorporated into a P(V) oxide, a non-transition metal, or the like. Incertain preferred embodiments, all non-donor atoms are carbon.

The term “macropolycyclic ligand” is used herein to refer to theessential ligand required for forming the essential metal catalyst. Asindicated by the term, such a ligand is both a macrocycle and ispolycyclic. “Polycyclic” means at least bicyclic in the conventionalsense. The essential macropolycyclic ligands must be rigid, andpreferred ligands must also cross-bridged.

Non-limiting examples of macropolycyclic rigid ligands, as definedherein, include 1.3-1.7:

Ligand 1.3 is a macropolycylic rigid ligand in accordance with theinvention which is a highly preferred, cross-bridged, methyl-substituted(all nitrogen atoms tertiary) derivative of cyclam. Formally, thisligand is named 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneusing the extended von Baeyer system. See “A Guide to IUPAC Nomenclatureof Organic Compounds: Recommendations 1993”, R. Panico, W. H. Powell andJ- C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; seeespecially section R-2.4.2.1. According to conventional terminology, N1and N8 are “bridgehead atoms”; as defined herein, more particularly“bridgehead donor atoms” since they have lone pairs capable of donationto a metal. N1 is connected to two non-bridgehead donor atoms, N5 andN12, by distinct saturated carbon chains 2,3,4 and 14,13 and tobridgehead donor atom N8 by a “linking moiety” a,b which here is asaturated carbon chain of two carbon atoms. N8 is connected to twonon-bridgehead donor atoms, N5 and N12, by distinct chains 6,7 and9,10,11. Chain a,b is a “linking moiety” as defined herein, and is ofthe special, preferred type referred to as a “cross-bridging” moiety.The “macrocyclic ring” of the ligand supra, or “main ring” (IUPAC),includes all four donor atoms and chains 2,3,4; 6,7; 9,10,11 and 13,14but not a,b. This ligand is conventionally bicyclic. The short bridge or“linking moiety” a,b is a “cross-bridge” as defined herein, with a,bbisecting the macrocyclic ring.

Ligand 1.4 lies within the general definition of macropolycyclic rigidligands as defined herein, but is not a preferred ligand since it is not“cross-bridged” as defined herein. Specifically, the “linking moiety”a,b connects “adjacent” donor atoms N1 and N12, which is outside thepreferred embodiment of the present invention: see for comparison thepreceding macrocyclic rigid ligand, in which the linking moiety a,b is across-bridging moiety and connects “non-adjacent” donor atoms.

Ligand 1.5 lies within the general definition of macropolycyclic rigidligands as defined herein, but is not a preferred ligand since itcontains only three donor atoms, all of which are bridgehead donoratoms.

Ligand 1.6 lies within the general definition of macropolycylic rigidligands as defined herein. This ligand can be viewed as a “main ring”which is a tetraazamacrocycle having three bridgehead donor atoms. Thismacrocycle is bridged by a “linking moiety” having a structure morecomplex than a simple chain, containing as it does a secondary ring. Thelinking moiety includes both a “cross-bridging” mode of bonding, and anon-cross-bridging mode.

Ligand 1.7 lies within the general definition of macropolycylic rigidligands. Five donor atoms are present; two being bridgehead donor atoms.This ligand is a preferred cross-bridged ligand. It contains noexocyclic or pendant substituents which have aromatic content.

In contrast, for purposes of comparison, the following ligands (1.8 and1.9) conform neither with the broad definition of macropolycyclic rigidligands in the present invention, nor with the preferred cross-bridgedsub-family thereof and therefore are completely outside the presentinvention

In the ligand supra, neither nitrogen atom is a bridgehead donor atom.There are insufficient donor atoms.

The ligand supra is also outside the present invention. The nitrogenatoms are not bridgehead donor atoms, and the two-carbon linkage betweenthe two main rings does not meet the invention definition of a “linkingmoiety” since, instead of linking across a single macrocycle ring, itlinks two different rings. The linkage therefore does not conferrigidity as used in the term “macropolycyclic rigid ligand”. See thedefinition of “linking moiety” hereinafter.

Generally, the essential macropolycyclic rigid ligands (and thecorresponding transition-metal catalysts) herein comprise:

(a) at least one macrocycle main ring comprising three or moreheteroatoms; and

(b) a covalently connected non-metal superstructure capable ofincreasing the rigidity of the macrocycle, preferably selected from

(i) a bridging superstructure, such as a linking moiety;

(ii) a cross-bridging superstructure, such as a cross-bridging linkingmoiety; and

(iii) combinations thereof.

The term “superstructure” is used herein as defined by Busch et al., inthe Chemical Reviews article incorporated hereinabove.

Preferred superstructures herein not only enhance the rigidity of theparent macrocycle, but also favor folding of the macrocycle so that itco-ordinates to a metal in a cleft. Suitable superstructures can beremarkably simple, for example a linking moiety such as any of thoseillustrated in 1.10 and 1.11 below, can be used.

wherein n is an integer, for example from 2 to 8, preferably less than6, typically 2 to 4, or

wherein m and n are integers from about 1 to 8, more preferably from 1to 3; Z is N or CH; and T is a compatible substituent, for example H,alkyl, trialkylammonium, halogen, nitro, sulfonate, or the like. Thearomatic ring in 1.11 can be replaced by a saturated ring, in which theatom in Z connecting into the ring can contain N, O, S or C.

Without intending to be limited by theory, it is believed that thepreorganization built into the macropolycyclic ligands herein that leadsto extra kinetic and/or thermodynamic stability of their metal complexesarises from either or both of topological constraints and enhancedrigidity (loss of flexibility) compared to the free parent macrocyclewhich has no superstructure. The macropolycyclic rigid ligands asdefined herein and their preferred cross-bridged sub-family, which canbe said to be “ultra-rigid”, combine two sources of fixedpreorganization. In preferred ligands herein, the linking moieties andparent macrocycle rings are combined to form ligands which have asignificant extent of “fold”, typically greater than in many knownsuperstructured ligands in which a superstructure is attached to alargely planar, often unsaturated macrocycle. See, for example, : D. H.Busch, Chemical Reviews, (1993), 93, 847-880. Further, the preferredligands herein have a number of particular properties, including (1)they are characterized by very high proton affinities, as in so-called“proton sponges”; (2) they tend to react slowly with multivalenttransition metals, which when combined with (1) above, renders synthesisof their complexes with certain hydrolyzable metal ions difficult inhydroxylic solvents; (3) when they are coordinated to transition metalatoms as identified herein, the ligands result in complexes that haveexceptional kinetic stability such that the metal ions only dissociateextremely slowly under conditions that would destroy complexes withordinary ligands; and (4) these complexes have exceptional thermodynamicstability; however, the unusual kinetics of ligand dissociation from thetransition metal may defeat conventional equilibrium measurements thatmight quantitate this property.

Other usable but more complex superstructures suitable for the presentinvention purposes include those containing an additional ring, such asin 1.6. Other bridging superstructures when added to a macrocycleinclude, for example, 1.4. In contrast, cross-bridging superstructuresunexpectedly produce a substantial improvement in the utility of amacrocyclic ligand for use in oxidation catalysis: a preferredcross-bridging superstructure is 1.3. A superstructure illustrative of abridging plus cross-bridging combination is 1.12:

In 1.12, linking moiety (i) is cross-bridging, while linking moiety (ii)is not. 1.12 is less preferred than 1.3.

More generally, a “linking moiety”, as defined herein, is a covalentlylinked moiety comprising a plurality of atoms which has at least twopoints of covalent attachment to a macrocycle ring and which does notform part of the main ring or rings of the parent macrocycle. In otherterms, with the exception of the bonds formed by attaching it to theparent macrocycle, a linking moiety is wholly in a superstructure.

The terms “cross-bridged” or “cross-bridging”, as used herein, refers tocovalent ligation, bisection or “tying” of a macrocycle ring in whichtwo donor atoms of the macrocycle ring are covalently connected by alinking moiety, for example an additional chain distinct from themacrocycle ring, and further, preferably, in which there is at least onedonor atom of the macrocycle ring in each of the sections of themacrocycle ring separated by the ligation, bisection or tying.Cross-bridging is not present in structure 1.4 hereinabove; it ispresent in 1.3, where two donor atoms of a preferred macrocycle ring areconnected in such manner that there is not a donor atom in each of thebisection rings. Of course, provided that cross-bridging is present, anyother kind of bridging can optionally be added and the bridgedmacrocycle will retain the preferred property of being “cross-bridged”:see Structure 1.12. A “cross-bridged chain” or “cross-bridging chain”,as defined herein, is thus a highly preferred type of linking moietycomprising a plurality of atoms which has at least two points ofcovalent attachment to a macrocycle ring and which does not form part ofthe original macrocycle ring (main ring), and further, which isconnected to the main ring using the rule identified in defining theterm “cross-bridging”.

The term “adjacent” as used herein in connection with donor atoms in amacrocycle ring means that there are no donor atoms intervening betweena first donor atom and another donor atom within the macrocycle ring;all intervening atoms in the ring are non-donor atoms, typically theyare carbon atoms. The complementary term “non-adjacent” as used hereinin connection with donor atoms in a macrocycle ring means that there isat least one donor atom intervening between a first donor atom andanother that is being referred to. In preferred cases such as across-bridged tetraazamacrocycle, there will be at least a pair ofnon-adjacent donor atoms which are bridgehead atoms, and a further pairof non-bridgehead donor atoms.

“Bridgehead” atoms herein are atoms of a macropolycyclic ligand whichare connected into the structure of the macrocycle in such manner thateach non-donor bond to such an atom is a covalent single bond and thereare sufficient covalent single bonds to connect the atom termed“bridgehead” such that it forms a junction of at least two rings, thisnumber being the maximum observable by visual inspection in theun-coordinated ligand.

In general, the metal oxidation catalysts herein may contain bridgeheadatoms which are carbon, however, and importantly, in certain preferredembodiments, all essential bridgehead atoms are heteroatoms, allheteroatoms are tertiary, and further, they each co-ordinate throughlone pair donation to the metal. Thus, bridgehead atoms are junctionpoints not only of rings in the macrocycle, but also of chelate rings.

The term “a further donor atom” unless otherwise specifically indicated,as used herein, refers to a donor atom other than a donor atom containedin the macrocycle ring of an essential macropolycycle. For example, a“further donor atom” may be present in an optional exocyclic substituentof a macrocyclic ligand, or in a cross-bridged chain thereof. In certainpreferred embodiments, a “further donor atom” is present only in across-bridged chain.

The term “coordinated with the same transition metal” as used herein isused to emphasize that a particular donor atom or ligand does not bindto two or more distinct metal atoms, but rather, to only one.

Optional Ligands

It is to be recognized for the transition-metal oxidation catalystsuseful in the present invention catalytic systems that additionalnon-macropolycyclic ligands may optionally also be coordinated to themetal, as necessary to complete the coordination number of the metalcomplexed. Such ligands may have any number of atoms capable of donatingelectrons to the catalyst complex, but preferred optional ligands have adenticity of 1 to 3, preferably 1. Examples of such ligands are H₂O,ROH, NR₃, RCN, OH⁻, OOH⁻, RS⁻, RO⁻, RCOO⁻, OCN⁻, SCN⁻, N₃ ⁻, CN⁻, F⁻,Cl⁻, Br⁻, I⁻, O₂ ⁻, NO₃ ⁻, NO₂ ⁻, SO₄ ²⁻, SO₃ ²⁻, PO₄ ⁻³, organicphosphates, organic phosphonates, organic sulfates, organic sulfonates,and aromatic N donors such as pyridines, pyrazines, pyrazoles,imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles with Rbeing H, optionally substituted alkyl, optionally substituted aryl.Preferred transition-metal oxidation catalysts comprise one or twonon-macropolycyclic ligands.

The term “non-macropolycyclic ligands” is used herein to refer toligands such as those illustrated immediately hereinabove which ingeneral are not essential for forming the metal catalyst, and are notcross-bridged macropolycycles. “Not essential”, with reference to suchnon-macropolycyclic ligands means that, in the invention as broadlydefined, they can be substituted by a variety of common alternateligands. In highly preferred embodiments in which metal, macropolycyclicand non-macropolycyclic ligands are finely tuned into a transition-metaloxidation catalyst, there may of course be significant differences inperformance when the indicated non-macropolycyclic ligand(s) arereplaced by further, especially non-illustrated, alternative ligands.

The term “metal catalyst” or “transition-metal oxidation catalyst” isused herein to refer to the essential catalyst compound of the inventionand is commonly used with the “metal” qualifier unless absolutely clearfrom the context. Note that there is a disclosure hereinafter pertainingspecifically to optional catalyst materials. Therein the term “bleachcatalyst” may be used unqualified to refer to optional, organic(metal-free) catalyst materials, or to optional metal-containingcatalysts that lack the advantages of the essential catalyst: suchoptional materials, for example, include known metal porphyrins ormetal-containing photobleaches. Other optional catalytic materialsherein include enzymes.

The macropolycyclic rigid ligands of the inventive compositions andmethods also include ligands selected from the group consisting of:(i) the macropolycyclic rigid ligand of formula (I) having denticity of3 or, preferably, 4:

(ii) the macropolycyclic rigid ligand of formula (II) having denticityof 4 or 5:

(iii) the macropolycyclic rigid ligand of formula (III) having denticityof 5 or 6:

(iv) the macropolycyclic rigid ligand of formula (IV) having denticityof 6 or 7:

wherein in these formulas:each “E” is the moiety (CR_(n))_(a)-X-(CR_(n))_(a′), wherein X isselected from the group consisting of O, S, NR and P, or a covalentbond, and preferably X is a covalent bond and for each E the sum of a+a′is independently selected from I to 5, more preferably 2 and 3;each “G” is the moiety (CR_(n))_(b);each “R” is independently selected from H, alkyl, alkenyl, alkynyl,aryl, alkylaryl (e.g., benzyl), and heteroaryl, or two or more R arecovalently bonded to form an aromatic, heteroaromatic, cycloalkyl, orheterocycloalkyl ring;each “D” is a donor atom independently selected from the groupconsisting of N, O, S, and P, and at least two D atoms are bridgeheaddonor atoms coordinated to the transition metal;“B” is a carbon atom or “D” donor atom, or a cycloalkyl or heterocyclicring;each “n” is an integer independently selected from 1 and 2, completingthe valence of the carbon atoms to which the R moieties are covalentlybonded;each “n”′ is an integer independently selected from 0 and 1, completingthe valence of the D donor atoms to which the R moieties are covalentlybonded;each “n”″ is an integer independently selected from 0, 1, and 2completing the valence of the B atoms to which the R moieties arecovalently bonded;each “a” and “a”′ is an integer independently selected from 0-5,preferably a+a′ equals 2 or 3, wherein the sum of all “a” plus “a”′ inthe ligand of formula (I) is within the range of from about 7 to about12, the sum of all “a” plus “a”′ in the ligand of formula (II) is withinthe range of from about 6 (preferably 8) to about 12, the sum of all “a”plus “a”′ in the ligand of formula (III) is within the range of fromabout 8 (preferably 10) to about 15, and the sum of all “a” plus “a”′ inthe ligand of formula (IV) is within the range of from about 10(preferably 12) to about 18;each “b” is an integer independently selected from 0-5, or in any of theabove formulas, one or more of the (CR_(n))_(b) moieties covalentlybonded from any D to the B atom is absent as long as at least two(CR_(n))_(b) covalently bond two of the D donor atoms to the B atom inthe formula, and the sum of all “b” is within the range of from about 1to about 5. Preferred ligands of the above formulas are those which arecross-bridged macropolycyclic ligands having Formulas (II), (III) or(IV).

It is to be noted herein that for the above formulas wherein “a” or “a”′is 1, these ligands are not preferred for potential instability reasonsin selected solvents, but are still within the scope of the presentinvention.

Preferred are the transition-metal oxidation catalysts wherein in thecross-bridged macropolycyclic ligand the D and B are selected from thegroup consisting of N and O, and preferably all D are N. Also preferredare wherein in the cross-bridged macropolycyclic ligand all “a” areindependently selected from the integers 2 and 3, all X are selectedfrom covalent bonds, all “a”′ are 0, and all “b” are independentlyselected from the integers 0, 1, and 2. Tetradentate and pentadentatecross-bridged macropolycyclic ligands are most preferred.

Unless otherwise specified, the convention herein when referring todenticity, as in “the macropolycycle has a denticity of four” will be torefer to a characteristic of the ligand: namely, the maximum number ofdonor bonds that it is capable of forming when it coordinates to ametal. Such a ligand is identified as “tetradentate”. Similarly, amacropolycycle containing five nitrogen atoms each with a lone pair isreferred to as “pentadentate”. The present invention encompassescatalytic systems in which the macrocyclic rigid ligand exerts its fulldenticity, as stated, in the transition-metal catalyst complexes;moreover, the invention also encompasses any equivalents which can beformed, for example, if one or more donor sites are not directlycoordinated to the metal. This can happen, for example, when apentadentate ligand coordinates through four donor atoms to thetransition metal and one donor atom is protonated.

The further to illustrate preferred catalytic systems, the inventionalso includes those containing metal catalysts wherein the cross-bridgedmacropolycyclic ligand is a bicyclic ligand; preferably thecross-bridged macropolycyclic ligand is a macropolycyclic moiety offormula (II) having the formula:

wherein each “a” is independently selected from the integers 2 or 3, andeach “b” is independently selected from the integers 0, 1 and 2.

Further preferred are the compositions containing cross-bridgedmacropoly-cyclic ligands having the formula:

wherein in this formula:each “n” is an integer independently selected from 1 and 2, completingthe valence of the carbon atom to which the R moieties are covalentlybonded;each “R” and “R¹” is independently selected from H, alkyl, alkenyl,alkynyl, aryl, alkylaryl (e.g., benzyl) and heteroaryl, or R and/or R¹are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl,or heterocycloalkyl ring, and wherein preferably all R are H and R¹ areindependently selected from linear or branched, substituted orunsubstituted C₁-C₂₀ alkyl, alkenyl or alkynyl;each “a” is an integer independently selected from 2 or 3;preferably all nitrogen atoms in the cross-bridged macropolycycle ringsare coordinated with the transition metal.

The invention further includes the novel methods, compositions, andtransition-metal catalysts which include the transition-metal complexes,preferably the Mn, Fe and Cr complexes, or preferred cross-bridgedmacropolycyclic ligands having the formula:

wherein in this formula “R¹” is independently selected from H, andlinear or branched, substituted or unsubstituted C₁-C₂₀ alkyl,alkylaryl, alkenyl or alkynyl, more preferably R¹ is alkyl or alkylaryl;and preferably all nitrogen atoms in the macropolycyclic rings arecoordinated with the transition metal.

Also preferred are cross-bridged macropolycyclic ligands having theformula:

wherein in this formula:each “n” is an integer independently selected from 1 and 2, completingthe valence of the carbon atom to which the R moieties are covalentlybonded;each “R” and “R¹” is independently selected from H, alkyl, alkenyl,alkynyl, aryl, alkylaryl (e.g., benzyl), and heteroaryl, or R and/or R¹are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl,or heterocycloalkyl ring, and wherein preferably all R are H and R¹ areindependently selected from linear or branched, substituted orunsubstituted C₁-C₂₀ alkyl, alkenyl or alkynyl;each “a” is an integer independently selected from 2 or 3;preferably all nitrogen atoms in the macropolycyclic rings arecoordinated with the transition metal. In terms of the presentinvention, even though any of such ligands are known, the inventionencompasses the use of these ligands in the form of theirtransition-metal complexes as oxidation catalysts, or in the form of thedefined catalytic systems.

In like manner, included in the definition of the preferredcross-bridged macropolycyclic ligands are those having the formula:

wherein in either of these formulae, “R¹” is independently selected fromH, or, preferably, linear or branched, substituted or unsubstitutedC₁-C₂₀ alkyl, alkenyl or alkynyl; and preferably all nitrogen atoms inthe macropolycyclic rings are coordinated with the transition metal.

The present invention has numerous variations and alternate embodimentswhich do not depart from its spirit and scope. Thus, in the foregoingcatalytic systems, the macropolycyclic ligand can be replaced by any ofthe following:

In the above, the R, R′, R″, R′″ moieties can, for example, be methyl,ethyl or propyl. (Note that in the above formalism, the short straightstrokes attached to certain N atoms are an alternate representation fora methyl group).

While the above illustrative structures involve tetra-aza derivatives(four donor nitrogen atoms), ligands and the corresponding complexes inaccordance with the present invention can also be made, for example fromany of the following:

Moreover, using only a single organic macropolycycle, preferably across-bridged derivative of cyclam, a wide range of oxidation catalystcompounds of the invention may be prepared; numerous of these arebelieved to be novel chemical compounds. Preferred transition-metalcatalysts of both cyclam-derived and non-cyclam-derived cross-bridgedkinds are illustrated, but not limited, by the following:

In other embodiments of the invention, transition-metal complexes, suchas the Mn, Fe or Cr complexes, especially (II) and/or (III) oxidationstate complexes, of the hereinabove-identified metals with any of thefollowing ligands are also included:

wherein R¹ is independently selected from H (preferably non-H) andlinear or branched, substituted or unsubstituted C₁-C₂₀ alkyl, alkenylor alkynyl and L is any of the linking moieties given herein, forexample 1.10 or 1.11;

wherein R¹ is as defined supra; m,n,o and p can vary independently andare integers which can be zero or a positive integer and can varyindependently while respecting the provision that the sum m+n+o+p isfrom 0 to 8 and L is any of the linking moieties defined herein;

wherein X and Y can be any of the R¹ defined supra, m,n,o and p are asdefined supra and q is an integer, preferably from 1 to 4; or, moregenerally,

wherein L is any of the linking moieties herein, X and Y can be any ofthe R¹ defined supra, and m,n,o and p are as defined supra. Alternately,another useful ligand is:

wherein R¹ is any of the R¹ moieties defined supra.

Pendant Moieties

Macropolycyclic rigid ligands and the corresponding transition-metalcomplexes and oxidation catalytic systems herein may also incorporateone or more pendant moieties, in addition to, or as a replacement for,R¹ moieties. Such pendant moieties are nonlimitingly illustrated by anyof the following:

-   -   —(CH₂)_(n)—CH₃ —(CH₂)_(n)—C(O)NH₂    -   —(CH₂)_(n)—CN —(CH₂)_(n)—C(O)OH    -   —(CH₂)_(n)—C(O)NR₂ —(CH₂)_(n)—OH    -   —(CH₂)_(n)—C(O)OR        wherein R is, for example, a C1-C12 alkyl, more typically a        C1-C4 alkyl, and Z and T are as defined in 1.11. Pendant        moieties may be useful, for example, if it is desired to adjust        the solubility of the catalyst in a particular solvent adjunct.

Alternately, complexes of any of the foregoing highly rigid,cross-bridged macropolycyclic ligands with any of the metals indicatedare equally within the invention.

Preferred are catalysts wherein the transition metal is selected frommanganese and iron, and most preferably manganese. Also preferred arecatalysts wherein the molar ratio of transition metal to macropolycyclicligand in the oxidation catalyst is 1:1, and more preferably wherein thecatalyst comprises only one metal per oxidation catalyst complex.Further preferred transition-metal oxidation catalysts are monometallic,mononuclear complexes. The term “monometallic, mononuclear complex” isused herein in referring to an essential transition-metal oxidationcatalyst compound to identify and distinguish a preferred class ofcompounds containing only one metal atom per mole of compound and onlyone metal atom per mole of cross-bridged macropolycyclic ligand.

Preferred transition-metal oxidation catalysts also include thosewherein at least four of the donor atoms in the macropolycyclic rigidligand, preferably at least four nitrogen donor atoms, two of which forman apical bond angle with the same transition metal of 180±50° and twoof which form at least one equatorial bond angle of 90±20°. Suchcatalysts preferably have four or five nitrogen donor atoms in total andalso have coordination geometry selected from distorted octahedral(including trigonal antiprismatic and general tetragonal distortion) anddistorted trigonal prismatic, and preferably wherein further thecross-bridged macropolycyclic ligand is in the folded conformation (asdescribed, for example, in Hancock and Martell, Chem. Rev., 1989, 89, atpage 1894). A folded conformation of a cross-bridged macropolycyclicligand in a transition-metal complex is further illustrated below:

This catalyst is the complex of Example 1 hereinafter. The center atomis Mn; the two ligands to the right are chloride; and a Bcyclam ligandoccupies the left side of the distorted octahedral structure. Thecomplex contains an angle N-Mn-N of 158° incorporating the two mutuallytrans-donor atoms in “axial” positions; the corresponding angle N—Mn—Nfor the nitrogen donor atoms in plane with the two chloride ligands is83.2°.

Stated alternately, the preferred synthetic, laundry, cleaning,papermaking, or effluent-treating catalytic systems herein containtransition-metal complexes of a macropolycyclic ligand in which there isa major energetic preference of the ligand for a folded, as distinctfrom an “open” and/or “planar” and or “flat” conformation. Forcomparison, a disfavored conformation is, for example, either of thetrans-structures shown in Hancock and Martell, Chemical Reviews, (1989),89 at page 1894 (see FIG. 18), incorporated by reference.

In light of the foregoing coordination description, the presentinvention includes oxidation catalytic systems comprising atransition-metal oxidation catalyst, especially based on Mn(II) orMn(III) or correspondingly, Fe(II) or Fe(III) or Cr(II) or Cr(III),wherein two of the donor atoms in the macropolycyclic rigid ligand,preferably two nitrogen donor atoms, occupy mutually trans- positions ofthe coordination geometry, and at least two of the donor atoms in themacropolycyclic rigid ligand, preferably at least two nitrogen donoratoms, occupy cis-equatorial positions of the coordination geometry,including particularly the cases in which there is substantialdistortion as illustrated hereinabove.

The present catalytic systems can, furthermore, include transition metaloxidation catalysts in which the number of asymmetric sites can varywidely; thus both S- and R-absolute conformations can be included forany stereochemically active site. Other types of isomerism, such asgeometric isomerism, are also included. The transition-metal oxidationcatalyst can further include mixtures of geometric or stereoisomers.

Purification of Catalyst

In general, the state of purity of the transition-metal oxidationcatalyst can vary, provided that any impurities, such as byproducts ofthe synthesis, free ligand(s), unreacted transition-metal saltprecursors, colloidal organic or inorganic particles, and the like, arenot present in amounts which substantially decrease the utility of thetransition-metal oxidation catalyst. It has been discovered thatpreferred embodiments of the present invention include those in whichthe transition-metal oxidation catalyst is purified by any suitablemeans, such that it does not excessively consume available oxygen (AvO).Excessive AvO consumption is defined as including any instance ofexponential decrease in AvO levels of bleaching, oxidizing or catalyzingsolutions with time at 20-40 deg. C. Preferred transition-metaloxidation catalysts herein, whether purified or not, when placed intodilute aqueous buffered alkaline solution at a pH of about 9(carbonate/bicarbonate buffer) at temperatures of about 40 deg. C., havea relatively steady decrease in AvO levels with time; in preferredcases, this rate of decrease is linear or approximately linear. In thepreferred embodiments, there is a rate of AvO consumption at 40 deg C.given by a slope of a graph of % AvO vs. time (in sec.) (hereinafter“AvO slope”) of from about −0.0050 to about −0.0500, more preferably−0.0100 to about −0.0200. Thus, a preferred Mn(II) oxidation catalyst inaccordance with the invention has an AvO slope of from about −0.0140 toabout −0.0182; in contrast, a somewhat less preferred transition metaloxidation catalyst has an AvO slope of −0.0286.

Preferred methods for determining AvO consumption in aqueous solutionsof transition metal oxidation catalysts herein include the well-knowniodometric method or its variants, such as methods commonly applied forhydrogen peroxide. See, for example, Organic Peroxides, Vol. 2., D.Swern (Ed.,), Wiley-Interscience, New York, 1971, for example the tableat p. 585 and references therein including P. D. Bartlett and R.Altscul, J. Amer. Chem. Soc., 67, 812 (1945) and W. E. Cass, J. Amer.Chem. Soc., 68, 1976 (1946). Accelerators such as ammonium molybdate canbe used. The general procedure used herein is to prepare an aqueoussolution of catalyst and hydrogen peroxide in a mild alkaline buffer,for example carbonate/bicarbonate at pH 9, and to monitor theconsumption of hydrogen peroxide by periodic removal of aliquots of thesolution which are “stopped” from further loss of hydrogen peroxide byacidification using glacial acetic acid, preferably with chilling (ice).These aliquots can then be analyzed by reaction with potassium iodide,optionally but sometimes preferably using ammonium molybdate (especiallylow-impurity molybdate, see for example U.S. Pat. No. 4,596,701) toaccelerate complete reaction, followed by back-titratation using sodiumthiosulfate. Other variations of analytical procedure can be used, suchas thermometric procedures, potential buffer methods (Ishibashi et al.,Anal. Chim. Acta (1992), 261(1-2), 405-10) or photometric procedures fordetermination of hydrogen peroxide (EP 485,000 A2, May 13, 1992).Variations of methods permitting fractional determinations, for exampleof peracetic acid and hydrogen peroxide, in presence or absence of theinstant transition-metal oxidation catalysts are also useful; see, forexample JP 92-303215, Oct. 16, 1992.

In another embodiment of the present invention, there are encompassedlaundry and cleaning compositions incorporating transition-metaloxidation catalysts which have been purified to the extent of having adifferential AvO loss reduction, relative to the untreated catalyst, ofat least about 10% (units here are dimensionless since they representthe ratio of the AvO slope of the treated transition-metal oxidationcatalyst over the AvO slope for the untreated transition metal oxidationcatalyst - effectively a ratio of AvO's). In other terms, the AvO slopeis improved by purification so as to bring it into the above-identifiedpreferred ranges.

In yet another embodiment of the instant invention, two processes havebeen identified which are particularly effective in improving thesuitability of transition-metal oxidation catalysts, as synthesized, forincorporation into laundry and cleaning products or for other usefuloxidation catalysis applications. One such process is any process havinga step of treating the transition-metal oxidation catalyst, as prepared,by extracting the transition-metal oxidation catalyst, in solid form,with an aromatic hydrocarbon solvent; suitable solvents areoxidation-stable under conditions of use and include benzene andtoluene, preferably toluene. Surprisingly, toluene extraction canmeasurably improve the AvO slope (see disclosure hereinabove).

Another process which can be used to improve the AvO slope of thetransition metal oxidation catalyst is to filter a solution thereofusing any suitable filtration means for removing small or colloidalparticles. Such means include the use of fine-pore filters;centrifugation; or coagulation of the colloidal solids.

In more detail, a full procedure for purifying a transition-metaloxidation catalyst herein can include:

(a) dissolving the transition-metal oxidation catalyst, as prepared, inhot acetonitrile:

(b) filtering the resulting solution hot, e.g., at about 70 deg. C.,through glass microfibers (for example glass microfiber filter paperavailable from Whatman);

(c) if desired, filtering the solution of the first filtration through a0.2 micron membrane (for example, a 0.2 micron filter commerciallyavailable from Millipore) or centrifuging whereby colloidal particlesare removed;

(d) evaporating the solution of the second filtration to dryness;

(e) washing the solids of step (d) with toluene, for example five timesusing toluene in an amount which is double the volume of the oxidationcatalyst solids;

(f) drying the product of step (e).

Another procedure which can be used, in any convenient combination witharomatic solvent washes and/or removal of fine particles isrecrystallization. Recrystallization, for example of Mn(II) Bcyclamchloride transition-metal oxidation catalyst, can be done from hotacetonitrile. Recrystallization can have its disadvantages, for exampleit may on occasion be more costly.

Catalytic Systems and Methods for Synthetic Oxidation Reactions

Methods and catalytic systems for oxidizing alkenes to epoxides bytreating the alkene with a transition-metal complex are known, forexample from U.S. Pat. No. 5,428,180 and U.S. Pat. No. 5,077,394.Epoxidations of olefins can also be carried out according to the methodof Collman, J. P.; Kodadek, T. J.; Raybuck, S. A.; and Meunier, B.,Proc. Natl. Acad. Sci. U.S.A (1983), 80, 7039, and which publication isincorporated herein by reference in its entirety. In the presentinvention, catalytic systems and methods require the presence of thetransition-metal oxidation catalysts described herein to effect suchoxidative processes.

The catalytic systems for use herein suitably comprise atransition-metal oxidation catalyst as described herein, a primaryoxidation agent or primary oxidant, for example monopersulfate orperacetic acid or their salts, and a solvent. A wide range of protic andaprotic solvents can be used, covering a range of dielectric constants.The catalytic systems include solutions comprising at least about0.00001%, more preferably at least about 0.0001% of transition-metalcatalyst, from about 0.0001% to about 10%, by weight of primaryoxidation agent, and at least about 5%, more typically at least about50% of solvent. The amount of substrate (the compound to be oxidized)can vary in a wide range, in terms of proportion by weight to thecatalytic system. A suitable range of composition is from 1:10,000 toabout 10,000:1 of catalytic system to substrate by weight, moretypically from about 1:1,000 to about 1:1.

Similarly, other oxidation reactions for synthetic chemicalmanufacturing processes such as oxidation of sulfides to sulfones arecarried out according to the present invention utilizing catalyticsystems containing oxidation agent, transition-metal catalysts, andproportions of the materials as described herein. Again, it is preferredthat such processes use catalytic systems which are solutions of theseagents.

Catalytic systems and Methods for Pulp Oxidation

The application of oxidizing agents in a sequence of delignifying andbleaching treatment stages of unbleached chemical paper pulp processesare known, for example U.S. Pat. No. 5,431,781. The present inventioncatalytic systems and methods further require the presence of thetransition-metal oxidation catalysts described herein to effect suchoxidative processes.

All types of wood used for the production of chemical pulps are suitablefor use in the process of the present invention. In particular, thisincludes those used for kraft pulps, namely the coniferous woods suchas, for example, the species of pines and firs and the deciduous woodssuch as, for example, yellow pine, beech, oak, eucalyptus and hornbeam.

Catalytic systems useful in pulp and paper treatment can, in general,have a range of composition similar to that described supra for organicsynthetic purposes. The substrate in this instance is paper orpaper-derived materials having an oxidizable component, such as lignin.

In more detail, transition-metal catalysts herein can be useful in asomewhat similar manner to the substituted porphyrin metal complexes ofDolphin (U.S. Pat. No. 5,077,394), though there can be additionaladvantages, for example improved flexibility in the control ofwater-solubility of catalyst as compared with certain porphyrin systems.Thus transition-metal complexes identified herein may be used in theform of catalyst systems including (a) the transition-metal catalyst,(b) primary oxidant, for example peracetate, persulfate or peroxide, and(c) solvent such as water though nonaqueous, especially polar aproticsolvents such as dimethylformamide, acetonitrile, dimethylsulfoxide,alcohols e.g., methanol, ethanol, chlorinated solvents such asdichloromethane, chloroform or the like or combinations of water andsuch organic solvents having a wide range in dielectric constant may beused, together providing catalytic systems for oxidation applicable to avariety of processes, for example those in which prior art optionallysubstituted phenyl porphyrins have been indicated as useful. Thetransition-metal catalysts which are the more water soluble areparticularly useful in those processes in which water solubility isdesired or required. Such processes include, by way of illustration, theoxidation of alkanes (including cycloalkanes), the oxidation of alkenes(including cycloalkenes), the oxidative conversion of lignin modelcompounds which are converted by the lignin modifying and degradingfungal enzymes also known as ligninases, the use in the modification ordegradation of lignin, and the use in the treating of wood in variousforms such as wood chips or pulp to assist in or effect pulping orbleaching.

Particular pulping-related processes of interest for the use of thewater soluble transition-metal complexes, for example the Mn(II) Bcyclamcomplexes, for assisting in or effecting a modification or degradationof lignin, include processes of making and oxidatively treating thewell-known mechanical pulps such as thermomechanical pulps and kraftpulps so as to effect bleaching.

The invention also provides transition-metal complexes having reducedwater-solubility, such as those in which the macrocycle ligand carriesone or more long-chain alkyl pendant substituents, and these may also beused in various commercial applications such as solvent pulping, forexample the known organosolv pulping process. Other uses include thedecomposition of organic contaminants in waste streams such as thechlorinated organic compounds in E1 effluent from the kraft pulpchlorine bleaching process.

Of particular interest is the use of the present transition-metalcatalysts, including the Fe, Mn (preferred for environmental reasons)and even Ni types as catalysts in the catalytic oxidation of alkanes(including cycloalkanes) for the hydroxylation of the same (or ultimateketo formation) and in the catalytic oxidation of alkenes (includingcycloalkenes) to form epoxides (epoxidation). Such hydroxylations andepoxidation are well-known reactions which are commonly carried out inan organic solvent which is redox-inert under the operating conditions,but water containing systems may also be used; hence both the watersoluble and water insoluble transition-metal complexes may be used insuch processes.

In general, the present transition-metal oxidant catalytic systems maybe used over a wide range of reaction temperatures including hightemperatures up to 150 deg. C. or even higher, and over a wide range ofpH's which may extend from about 1 to 14, more suitably from pH 2 to pH12; nonetheless, it is particularly desirable to use the catalysts atambient or near-ambient temperatures where energy economy is desired,and to use mild pH's, which are desirably safe for material handling.The present catalyst systems have the advantage of being useful undersuch conditions.

The present invention includes use of the identified transition-metaloxidation catalyst systems in the oxidative delignification ofwood-pulp. U.S. Pat. No. 5,552,019, for example, describes suchdelignification using polyoxometallates. The present catalyst systems,typically comprising (a) the transition-metal catalyst; (b) a primaryoxidant such as sodium hypochlorite or, more preferably, potassiummonopersulfate triple salt, the latter sold commercially as OXONE by DuPont and (c) pH-adjusting adjuncts can be used, especially at pH in therange from about 7.5 to about 9.5, under mild temperature conditions fordelignification purposes.

The present invention has numerous alternate embodiments andramifications. For example, in the laundry detergents and laundrydetergent additives field, the invention includes all manner ofbleach-containing or bleach additive compositions, including forexample, fully-formulated heavy-duty granular detergents containingsodium perborate or sodium percarbonate and/or a preformed peracidderivative such as OXONE as primary oxidant, the transition-metalcatalyst of the invention, a bleach activator such astetraacetylethylenediamine or a similar compound, with or withoutnonanoyloxybenzenesulfonate sodium salt, and the like.

Other suitable composition forms include laundry bleach additivepowders, granular or tablet-form automatic dishwashing detergents,scouring powders and bathroom cleaners. In the solid-form compositions,the catalytic system may lack solvent (water)—this is added by the useralong with the substrate (a soiled surface) which is to be cleaned (orcontains soil to be oxidized).

Other desirable embodiments of the instant invention include dentifriceor denture cleaning compositions. Suitable compositions to which thetransition-metal complexes herein can be added include the dentifricecompositions containing stabilized sodium percarbonate, see for exampleU.S. Pat. No. 5,424,060 and the denture cleaners of U.S. Pat. No.5,476,607 which are derived from a mixture containing a pregranulatedcompressed mixture of anhydrous perborate, perborate monohydrate andlubricant, monopersulfate, non-granulated perborate monohydrate,proteolytic enzyme and sequestering agent, though enzyme-freecompositions are also very effective. Optionally, excipients, builders,colors, flavors, and surfactants can be added to such compositions,these being adjuncts characteristic of the intended use. RE Pat. No.32,771 describes another denture cleaning composition to which theinstant transition-metal catalysts may profitably be added. Thus, bysimple admixture of, for example, about 0.00001% to about 0.1% of thepresent transition-metal catalyst, a cleaning composition is securedthat is particularly suited for compaction into tablet form; thiscomposition also comprises a phosphate salt, an improved perborate saltmixture wherein the improvement comprises a combination of anhydrousperborate and monohydrate perborate in the amount of about 50% to about70% by weight of the total cleansing composition, wherein thecombination includes at least 20% by weight of the total cleansingcomposition of anhydrous perborate, said combination having a portionpresent in a compacted granulated mixture with from about 0.01% to about0.70% by weight of said combination of a polymeric fluorocarbon, and achelating or sequestering agent present in amounts greater than about10% by weight up to about 50% by weight of the total composition, saidcleansing composition being capable of cleansing stained surfaces andthe like with a soaking time of five minutes or less when dissolved inaqueous solution and producing a marked improvement in clarity ofsolution upon disintegration and cleaning efficacy over the prior art.Of course, the denture cleaning composition need not extend to thesophistication of such compositions: adjuncts not essential to theprovision of catalytic oxidation such as the fluorinated polymer can beomitted if desired.

In another non-limiting illustration, the present transition-metalcatalyst can be added to an effervescent denture-cleaning compositioncomprising monoperphthalate, for example the magnesium salt thereof,and/or to the composition of U.S. Pat. No. 4,490,269 incorporated hereinby reference. Preferred denture cleansing compositions include thosehaving tablet form, wherein the tablet composition is characterized byactive oxygen levels in the range from about 100 to about 200 mg/tablet;and compositions characterized by fragrance retention levels greaterthan about 50% throughout a period of six hours or greater. See U.S.Pat. No. 5,486,304 incorporated by reference for more detail inconnection especially with fragrance retention.

The advantages and benefits of the instant invention include cleaningcompositions which have superior bleaching compared to compositions nothaving the selected transition-metal oxidation catalyst. The superiorityin bleaching is obtained using very low levels of transition-metaloxidation catalyst. The invention includes embodiments which areespecially suited for fabric washing, having a low tendency to damagefabrics in repeated washings. However, numerous other benefits can besecured; for example, compositions an be relatively more aggressive, asneeded, for example, in tough cleaning of durable hard surfaces, such asthe interiors of ovens, or kitchen surfaces having difficult-to-removefilms of soil. The compositions can be used both in “pre-treat” modes,for example to loosen dirt in kitchens or bathrooms; or in a “mainwash”mode, for example in fully-formulated heavy-duty laundry detergentgranules. Moreover, in addition to the bleaching and/or soil-removingadvantages, other advantages of the instant compositions include theirefficacy in improving the sanitary condition of surfaces ranging fromlaundered textiles to kitchen counter-tops and bathroom tiles. Withoutintending to be limited by theory, it is believed that the compositionscan help control or kill a wide variety of micro-organisms, includingbacteria, viruses, sub-viral particles and molds; as well as to destroyobjectionable non-living proteins and/or peptides such as certaintoxins.

The transition-metal oxidation catalysts useful herein may besynthesized by any convenient route. However, specific synthesis methodsare nonlimitingly illustrated in detail as follows, including asynthetic method according to the present invention wherein the catalystis prepared under strictly oxygen and hydroxyl-free conditions by use ofbis(pyridine) manganese (II) salts (e.g., chloride salt) to coordinatethe manganese into the macropolycyclic rigid ligand [see, for example,Example 1, Method I, and Example 7].

EXAMPLE 1

Synthesis of [Mn(Bcyclam)Cl₂]

(a) Method I.

“Bcyclam” (5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2] hexadecane) isprepared by a synthesis method described by G. R. Weisman, et al.,J.Amer.Chem.Soc., (1990), 112, 8604. Bcyclam (1.00 g., 3.93 mmol) isdissolved in dry CH₃CN (35 mL, distilled from CaH₂). The solution isthen evacuated at 15 mm until the CH₃CN begins to boil. The flask isthen brought to atmospheric pressure with Ar. This degassing procedureis repeated 4 times. Mn(pyridine)₂Cl₂ (1.12 g., 3.93 mmol), synthesizedaccording to the literature procedure of H. T. Witteveen et al., J.Inorg. Nucl. Chem., (1974), 36, 1535, is added under Ar. The cloudyreaction solution slowly begins to darken. After stirring overnight atroom temperature, the reaction solution becomes dark brown withsuspended fine particulates. The reaction solution is filtered with a0.2μ filter. The filtrate is a light tan color. This filtrate isevaporated to dryness using a rotoevaporator. After drying overnight at0.05 mm at room temperature, 1.35 g. off-white solid product iscollected, 90% yield. Elemental Analysis: % Mn, 14.45;% C, 44.22; % H,7.95; theoretical for [Mn(Bcyclam)Cl₂], MnC₁₄H₃₀N₄Cl₂, MW=380.26. Found:% Mn, 14.98; % C, 44.48; % H, 7.86; Ion Spray Mass Spectroscopy showsone major peak at 354 mu corresponding to [Mn(Bcyclam)(formate)]⁺.

(b) Method II.

Freshly distilled Bcyclam (25.00 g., 0.0984 mol), which is prepared bythe same method as above, is dissolved in dry CH₃CN (900 mL, distilledfrom CaH₂). The solution is then evacuated at 15 mm until the CH₃CNbegins to boil. The flask is then brought to atmospheric pressure withAr. This degassing procedure is repeated 4 times. MnCl₂ (11.25 g.,0.0894 mol) is added under Ar. The cloudy reaction solution immediatelydarkens. After stirring 4 hrs. under reflux, the reaction solutionbecomes dark brown with suspended fine particulates. The reactionsolution is filtered through a 0.2μ filter under dry conditions. Thefiltrate is a light tan color. This filtrate is evaporated to drynessusing a rotoevaporator. The resulting tan solid is dried overnight at0.05 mm at room temperature. The solid is suspended in toluene (100 mL)and heated to reflux. The toluene is decanted off and the procedure isrepeated with another 100 mL of toluene. The balance of the toluene isremoved using a rotoevaporator. After drying overnight at 0.05 mm atroom temperature, 31.75 g. of a light blue solid product is collected,93.5% yield. Elemental Analysis: % Mn, 14.45; % C, 44.22; %H, 7.95; %N,14.73; % Cl, 18.65; theoretical for [Mn(Bcyclam)Cl₂], MnC₁₄H₃₀N₄Cl₂,MW=380.26. Found: % Mn, 14.69; % C, 44.69; % H, 7.99; % N, 14.78; % Cl,18.90 (Karl Fischer Water, 0.68%). Ion Spray Mass Spectroscopy shows onemajor peak at 354 mu corresponding to [Mn(Bcyclam)(formate)]⁺.

EXAMPLE 2

Synthesis of [Mn(C₄-Bcyclam)Cl₂] whereC₄-Bcyclam=5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

(a) C₄-Bcyclam Synthesis

Tetracyclic adduct I is prepared by the literature method of H. Yamamotoand K. Maruoka, J. Amer. Chem. Soc., (1981), 103, 4194. I (3.00 g., 13.5mmol) is dissolved in dry CH₃CN (50 mL, distilled from CaH₂).1-Iodobutane (24.84 g., 135 mmol) is added to the stirred solution underAr. The solution is stirred at room temperature for 5 days. 4-Iodobutane(12.42 g., 67.5 mmol) is added and the solution is stirred an additional5 days at RT. Under these conditions, I is fully mono-alkylated with1-iodobutane as shown by ¹³C-NMR. Methyl iodide (26.5 g, 187 mmol) isadded and the solution is stirred at room temperature for an additional5 days. The reaction is filtered using Whatman #4 paper and vacuumfiltration. A white solid, II, is collected (6.05 g., 82%). ¹³C NMR(CDCl₃) 16.3, 21.3, 21.6, 22.5, 25.8, 49.2, 49.4, 50.1, 51.4, 52.6,53.9, 54.1, 62.3, 63.5, 67.9, 79.1, 79.2 ppm. Electro spray Mass Spec.(MH⁺/2, 147).

II (6.00 g., 11.0 mmol) is dissolved in 95% ethanol (500 mL). Sodiumborohydride (11.0 g., 290 mmol) is added and the reaction turns milkywhite. The reaction is stirred under Ar for three days. Hydrochloricacid (100 mL, concentrated) is slowly dripped into the reaction mixtureover 1 hour. The reaction mixture is evaporated to dryness using arotoevaporator. The white residue is dissolved in sodium hydroxide (500mL, 1.00N). This solution is extracted with toluene (2×150 mL). Thetoluene layers are combined and dried with sodium sulfate. After removalof the sodium sulfate using filtration, the toluene is evaporated todryness using a rotoevaporator. The resulting oil is dried at roomtemperature under high vacuum (0.05 mm) overnight. A colorless oilresults 2.95 g., 90%. This oil (2.10 g.) is distilled using a short pathdistillation apparatus (still head temperature 115 C at 0.05 mm). Yield:2.00 g. ¹³C NMR (CDCl₃) 14.0, 20.6, 27.2, 27.7, 30.5, 32.5, 51.2, 51.4,54.1, 54.7, 55.1, 55.8, 56.1, 56.5, 57.9, 58.0, 59.9 ppm. Mass Spec.(MH⁺, 297).

(b) [Mn(C₄-Bcyclam)Cl₂] Synthesis

C₄-Bcyclam (2.00 g., 6.76 mmol) is slurried in dry CH₃CN (75 mL,distilled from CaH₂). The solution is then evacuated at 15 mm until theCH₃CN begins to boil. The flask is then brought to atmospheric pressurewith Ar. This degassing procedure is repeated 4 times. MnCl₂ (0.81 g.,6.43 mmol) is added under Ar. The tan, cloudy reaction solutionimmediately darkens. After stirring 4 hrs. under reflux, the reactionsolution becomes dark brown with suspended fine particulates. Thereaction solution is filtered through a 0.2μ membrane filter under dryconditions. The filtrate is a light tan color. This filtrate isevaporated to dryness using a rotoevaporator. The resulting white solidis suspended in toluene (50 mL) and heated to reflux. The toluene isdecanted off and the procedure is repeated with another 100 mL oftoluene. The balance of the toluene is removed using a rotoevaporator.After drying overnight at 0.05 mm, RT, 2.4 g. a light blue solidresults, 88% yield. Ion Spray Mass Spectroscopy shows one major peak at396 mu corresponding to [Mn(C₄-Bcyclam)(formate)]⁺.

EXAMPLE 3

Synthesis of [Mn(Bz-Bcyclam)Cl₂] whereBz-Bcyclam=5-benzyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

(a) Bz-Bcyclam Synthesis

This ligand is synthesized similarly to the C₄-Bcyclam synthesisdescribed above in Example 2(a) except that benzyl bromide is used inplace of the 1-iodobutane. ¹³C NMR (CDCl₃) 27.6, 28.4, 43.0, 52.1, 52.2,54.4, 55.6, 56.4, 56.5, 56.9, 57.3, 57.8, 60.2, 60.3, 126.7, 128.0,129.1, 141.0 ppm. Mass Spec. (MH⁺, 331).

(b) [Mn(Bz-Bcyclam)Cl₂] Synthesis

This complex is made similarly to the [Mn(C₄-Bcyclam)Cl₂] synthesisdescribed above in Example 2(b) except that Bz-Bcyclam is used in placeof the C₄-Bcyclam. Ion Spray Mass Spectroscopy shows one major peak at430 mu corresponding to [Mn(Bz-Bcyclam)(formate)]⁺.

EXAMPLE 4

Synthesis of [Mn(C₈-Bcyclam)Cl₂] whereC₈-Bcyclam=5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

(a) C₈-Bcyclam Synthesis:

This ligand is synthesized similarly to the C₄-Bcyclam synthesisdescribed above in Example 2(a) except that 1-iodooctane is used inplace of the 1-iodobutane. Mass Spec. (MH⁺, 353).

(b) [Mn(C₈-Bcyclam)Cl₂] Synthesis

This complex is made similarly to the [Mn(C₄-Bcyclam)Cl₂] synthesisdescribed above in Example 2(b) except that C₈-Bcyclam is used in placeof the C₄-Bcyclam. Ion Spray Mass Spectroscopy shows one major peak at452 mu corresponding to [Mn(B₈-Bcyclam)(formate)]⁺.

EXAMPLE 5

Synthesis of [Mn(H₂-Bcyclam)Cl₂] whereH₂-Bcyclam=1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

The H₂-Bcyclam is synthesized similarly to the C₄-Bcyclam synthesisdescribed above except that benzyl bromide is used in place of the1-iodobutane and the methyl iodide. The benzyl groups are removed bycatalytic hydrogenation. Thus, the resulting5,12-dibenzyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane and 10% Pd oncharcoal is dissolved in 85% acetic acid. This solution is stirred 3days at room temperature under 1 atm. of hydrogen gas. The solution isfiltered though a 0.2 micron filter under vacuum. After evaporation ofsolvent using a rotary evaporator, the product is obtained as acolorless oil. Yield: 90+%.

The Mn complex is made similarly to the [Mn(Bcyclam)Cl₂] synthesisdescribed in Example 1(b) except that the that H₂-Bcyclam is used inplace of the Bcyclam. Elemental Analysis: % C, 40.92; % H, 7.44; % N,15.91; theoretical for [Mn(H₂-Bcyclam)Cl₂], MnC₁₂H₂₆N₄Cl₂, MW=352.2.Found: % C, 41.00; % H, 7.60; % N, 15.80. FAB+Mass Spectroscopy showsone major peak at 317 mu corresponding to [Mn(H₂-Bcyclam)Cl]⁺ andanother minor peak at 352 mu corresponding to [Mn(H₂-Bcyclam)Cl₂]⁺.

EXAMPLE 6

Synthesis of [Fe(H₂-Bcyclam)Cl₂] whereH₂-Bcyclam=1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

The Fe complex is made similarly to the [Mn(H₂-Bcyclam)Cl₂] synthesisdescribed in Example 5 except that the that anhydrous FeCl₂ is used inplace of the MnCl₂.

Elemental Analysis: % C, 40.82; % H, 7.42; % N, 15.87; theoretical for[Fe(H₂-Bcyclam)Cl₂], FeC₁₂H₂₆N₄Cl₂, MW=353.1. Found: % C, 39.29; % H,7.49; % N, 15.00. FAB+Mass Spectroscopy shows one major peak at 318 mucorresponding to [Fe(H₂-Bcyclam)Cl]⁺and another minor peak at 353 mucorresponding to [Fe(H₂-Bcyclam)Cl₂]⁺.

EXAMPLE 7

Synthesis of:

Chloro-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaenemanganese(II) hexafluorophosphate ,7(b);Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaenemanganese(II) trifluoromethanesulfonate, 7(c) andThiocyanato-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaeneiron(II) thiocyanate, 7(d)

(a) Synthesis of the ligand20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaene

The ligand 7-methyl-3, 7, 11,17-tetraazabicyclo[11.3.1¹⁷]heptadeca-1(17), 13, 15-triene issynthesized by the literature procedure of K. P. Balakrishnan et al., J.Chem. Soc., Dalton Trans., 1990, 2965.

7-methyl-3, 7, 11, 17-tetraazabicyclo[ 11.3.1¹⁷]heptadeca-1(17), 13,15-triene (1.49 g, 6 mmol) and O,O′-bis(methanesulfonate)-2,6-pyridinedimethanol (1.77 g, 6 mmol) are separately dissolved in acetonitrile (60ml). They are then added via a syringe pump (at a rate of 1.2 ml/hour)to a suspension of anhydrous sodium carbonate (53 g, 0.5 mol) inacetonitrile (1380 ml). The temperature of the reaction is maintained at65° C. throughout the total reaction of 60 hours.

After cooling, the solvent is removed under reduced pressure and theresidue is dissolved in sodium hydroxide solution (200 ml, 4M). Theproduct is then extracted with benzene (6 times 100 ml) and the combinedorganic extracts are dried over anhydrous sodium sulfate. Afterfiltration the solvent is removed under reduced pressure. The product isthen dissolved in an acetonitrile/triethylamine mixture (95:5) and ispassed through a column of neutral alumina (2.5×12 cm). Removal of thesolvent yields a white solid (0.93 g, 44%).

This product may be further purified by recrystallization from anethanol/diethylether mixture combined with cooling at 0° C. overnight toyield a white crystalline solid. Anal. Calcd. for C₂₁H₂₉N₅: C, 71.75; H,8.32; N, 19.93. Found: C, 71.41; H, 8.00; N, 20.00. A mass spectrumdisplays the expected molecular ion peak [for C₂₁H₃₀N₅]+at m/z=352. The¹H NMR(400 MHz, in CD₃CN) spectrum exhibits peaks at δ=1.81 (m,4H); 2.19(s, 3H); 2.56 (t, 4H); 3.52 (t,4H); 3.68 (AB, 4H), 4.13 (AB, 4H), 6.53(d, 4H) and 7.07 (t, 2H). The ¹³C NMR(75.6 MHz, in CD₃CN) spectrum showseight peaks at δ=24.05, 58.52, 60.95, 62.94, 121.5, 137.44 and 159.33ppm.

All metal complexation reactions are performed in an inert atmosphereglovebox using distilled and degassed solvents.

(b) Complexation of the ligand L₁ with bis(pyridine) manganese (II)chloride

Bis(pyridine)manganese (II) chloride is synthesized according to theliterature procedure of H. T. Witteveen et al., J. Inorg. Nucl. Chem.,1974, 36, 1535.

The ligand L₁ (1.24 g, 3.5 mmol), triethylamine(0.35 g, 3.5 mmol) andsodium hexafluorophosphate (0.588 g, 3.5 mmol) are dissolved in pyridine(12 ml). To this is added bis(pyridine)manganese (II) chloride and thereaction is stirred overnight. The reaction is then filtered to remove awhite solid. This solid is washed with acetonitrile until the washingsare no longer colored and then the combined organic filtrates areevaporated under reduced pressure. The residue is dissolved in theminimum amount of acetonitrile and allowed to evaporate overnight toproduce bright red crystals. Yield: 0.8 g (39%). Anal. Calcd. forC₂₁H₃₁N₅Mn₁Cl₁P₁F₆: C, 43.00; H, 4.99 and N, 11.95. Found: C, 42.88; H,4.80 and N 11.86. A mass spectrum displays the expected molecular ionpeak [for C₂₁H₃₁N₅Mn₁Cl₁] at m/z=441. The electronic spectrum of adilute solution in water exhibits two absorption bands at 260 and 414 nm(ε=1.47×10³ and 773 M⁻¹cm⁻¹ respectively). The IR spectrum (KBr) of thecomplex shows a band at 1600 cm⁻¹ (pyridine), and strong bands at 840and 558 cm⁻¹ (PF₆-).

(c) Complexation of the ligand with manganese (II)trifluoromethanesulfonate

Manganese (II) trifluoromethanesulfonate is prepared by the literatureprocedure of Bryan and Dabrowiak, Inorg. Chem., 1975, 14, 297.

Manganese (II) trifluoromethanesulfonate (0.883 g, 2.5 mmol) isdissolved in acetonitrile (5 ml). This is added to a solution of theligand L₁(0.878 g, 2.5 mmol) and triethylamine (0.25 g, 2.5 mmol) inacetonitrile (5 ml). This is then heated for two hours before filteringand then after cooling removal of the solvent under reduced pressure.The residue is dissolved in a minimum amount of acetonitrile and left toevaporate slowly to yield orange crystals. Yield 1.06 g (60%). Anal.Calc. for Mn₁C₂₃H₂₉N₅S₂F₆O₆: C, 39.20; H, 4.15 and N, 9.95. Found: C,38.83; H, 4.35 and N, 10.10. The mass spectrum displays the expectedpeak for [Mn₁C₂₂H₂₉N₅S₁F₃O₃]⁺ at m/z=555. The electronic spectrum of adilute solution in water exhibits two absorption bands at 260 and 412 nm(ε=9733 and 607 M⁻¹cm⁻¹ respectively). The IR spectrum (KBr) of thecomplex shows a band at 1600 cm⁻¹ (pyridine) and 1260, 1160 and1030cm⁻¹(CF₃SO₃).

(d) Complexation of the ligand with iron (II) trifluoromethanesulfonateIron (II) trifluoromethanesulfonate is prepared in situ by theliterature procedure Tait and Busch, Inorg. Synth., 1978, XVIII, 7.

The ligand (0.833 g, 2.5 mmol) and triethylamine (0.505 g, 5 mmol) aredissolved in acetonitrile (5 ml). To this is added a solution ofhexakis(acetonitrile) iron (II) trifluoromethanesulfonate (1.5 g, 2.5mmol) in acetonitrile (5 ml) to yield a dark red solution. Sodiumthiocyanate (0.406 g, 5 mmol) is then added and the reaction stirred fora further hour. The solvent is then removed under reduced pressure andthe resulting solid is recrystallized from methanol to produce redmicrocrystals. Yield: 0.65 g (50%). Anal. Calc. for Fe₁C₂₃H₂₉N₇S₂:C,52.76; H, 5.59 and N, 18.74. Found: C 52.96; H, 5.53; N, 18.55. A massspectrum displays the expected molecular ion peak [for Fe₁C₂₂H₂₉N₆S₁]⁺at m/z=465. The ¹H NMR (300 MHz, CD₃CN) δ=1.70(AB,2H), 2.0 (AB,2H), 2.24(s,3H), 2.39 (m,2H), 2.70 (m,4H), 3.68 (m,4H), 3.95 (m,4H), 4.2 (AB,2H),7.09 (d,2H), 7.19 (d,2H), 7.52 (t,1H), 7.61 (d,1H). The IR spectrum(KBr) of the spectrum shows peaks at 1608 cm⁻¹ (pyridine) and strongpeaks at 2099 and 2037 cm⁻¹(SCN⁻). Example 8[Mn(Bcyclam)Cl₂] is used ina catalytic system including the transition metal complex, water assolvent, and t-butyl peroxide as primary oxidant, to catalyze theoxidation of a lignin model compound. See U.S. Pat. No. 5,077,394,Example 9, incorporated by reference, for details. The Mn complexreplaces the iron porphyrin complex of '394.

EXAMPLE 8

[Mn(Bcyclam)Cl₂] is used in a catalytic system including the transitionmetal complex, dimethylformamide as solvent, and peracetate as primaryoxidant, to catalyze the oxidation of lignin. See U.S. Pat. No.5,077,394, Example 10, incorporated by reference, for details. The Mncomplex replaces the iron porphyrin complex of this patent. In moredetail, 250 micrograms of the Kraft softwood lignin Indulin AT (WestvacoCorporation, Charleston Heights, S.C.) is dissolved in 2 ml DMF.Peracetic acid is used as the primary oxidant at a final concentrationof 1.84 micromolar. The Mn complex is used at a final concentration of500 micromolar. The reaction mixture is stirred at room temperature for24 hours and the resulting products are analyzed by gel permeationchromatography; any convenient column and solvent arrangement maysuffice, though a TSK 4000 column with 1:1 chloroform:dioxane(Phenomenex, Rancho Palos Verdes, Calif.) may be useful. Absorbance ismonitored at a suitable wavelength, for example 280 nm, and a distinctshift of the peaked area to the right indicates that a degradation oflignin has occurred.

EXAMPLE 9

[Mn(Bcyclam)Cl₂] is used in a catalytic system including the transitionmetal complex, water, and a range of different primary oxidants, tocatalyze the oxidation of veratryl alcohol to veratrylaldehyde. See U.S.Pat. No. 5,077,394, Example 11, incorporated by reference, for details.The Mn complex replaces the manganese porphyrin complex of this patent.The oxidants include hydrogen peroxide, sodium hypochlorite,t-butylhydroperoxide, cumylhydroperoxide, potassium iodate andiodosylbenzene and the experiments are carried out over a range of pH offrom 1 to 13 and with a variety of oxidant concentrations. The productis veratrylaldehyde. Yields tend to vary with pH and time, with evidenceof product formation being obtained under a variety of conditionsincluding slightly acid (e.g., pH 6.5) to mildly alkaline (e.g., pH8.5-9). The catalyst effects an improvement over non-catalyzed reaction.

EXAMPLE 10

[Mn(Bcyclam)Cl₂] is used in a catalytic system including the transitionmetal complex, solvent, and primary oxidant, to epoxidize cylohexene.See U.S. Pat. No. 5,077,394, Example 13, incorporated by reference, forone possible procedure. The Mn complex replaces the complexes used inthis patent.

EXAMPLE 11

[Mn(Bcyclam)C12] is used in a catalytic system including the transitionmetal complex, water as solvent, and hydrogen peroxide/peracetic acidbuffered in sodium carbonate/bicarbonate at pH of about 9, to oxidize ablue dye, suitably Chicago Sky Blue 6B (Aldrich), to a colorlessproduct. The reaction can be monitored by ultraviolet spectroscopy.

Oxidation Agents:

Oxidation agents (sometimes termed “oxidants”) useful in the presentinvention can be any of the oxidizing agents known for oxidativesynthetic reaction chemistry, pulp oxidation and bleaching, laundry,hard surface cleaning, automatic dishwashing or denture cleaningpurposes. Oxygen bleaches or mixtures thereof are preferred, thoughother oxidants, such as oxygen, an enzymatic hydrogen peroxide producingsystem, or hypohalites, such as chlorine oxidants like hypochlorite, mayalso be used. Oxygen-based oxidants deliver “available oxygen” (AvO) or“active oxygen” which is typically measurable by standard methods suchas iodide/thiosulfate and/or ceric sulfate titration. See the well-knownwork by Swern, or Kirk Othmer's Encyclopedia of Chemical Technologyunder “Bleaching Agents”. When the oxidant is a peroxygen compound, itcontains —O—O— linkages with one 0 in each such linkage being “active”.AvO content of such an oxidant compound, usually expressed as a percent,is equal to 100* the number of active oxygen atoms*(16/molecular weightof the oxygen bleach compound). Preferably, an oxygen bleach will beused herein, since this benefits most directly from combination with thecatalyst. The mode of combination can vary. For example, the catalystand oxidant can be incorporated into a single product formula, or can beused in various combinations of “pretreatment product” such as “stainsticks”, “main wash product” and even “post-wash product” such as fabricconditioners or dryer-added sheets. The oxidant herein can have anyphysical form compatible with the intended application; moreparticularly, liquid-form and solid-form oxidants as well as adjuncts,promoters or activators are included. Liquids can be included in soliddetergents, for example by adsorption onto an inert support; and solidscan be included in liquid detergents, for example by use of compatiblesuspending agents. Common oxidants of the peroxygen type includehydrogen peroxide, inorganic peroxohydrates, organic peroxohydrates andthe organic peroxyacids, including hydrophilic and hydrophobic mono- ordi-peroxyacids. These can be peroxycarboxylic acids, peroxyimidic acids,amidoperoxycarboxylic acids, or their salts including the calcium,magnesium, or mixed-cation salts. Peracids of various kinds can be usedboth in free form and as precursors known as “bleach activators” or“bleach promoters” which, when combined with a source of hydrogenperoxide, perhydrolyze to release the corresponding peracid. Also usefulherein as oxidants are the inorganic peroxides such as Na₂O₂,superoxides such as KO₂, organic hydroperoxides such as cumenehydroperoxide and t-butyl hydroperoxide, and the inorganic peroxoacidsand their salts such as the peroxosulfuric acid salts, especially thepotassium salts of peroxodisulfuric acid and, more preferably, ofperoxomonosulfuric acid including the commercial triple-salt form soldas OXONE by Dupont and also any equivalent commercially available formssuch as CUROX from Akzo or CAROAT from Degussa. Certain organicperoxides, such as dibenzoyl peroxide, may be useful, especially asadditives rather than as primary oxygen bleach.

Mixed oxidants are generally useful, as are mixtures of any oxidantswith the known bleach activators, organic catalysts, enzymatic catalystsand mixtures thereof; moreover such mixtures may further includebrighteners, photobleaches and dye transfer inhibitors of typeswell-known in the art.

Preferred oxidants include the peroxohydrates, sometimes known asperoxyhydrates or peroxohydrates. These are organic or, more commonly,inorganic salts capable of releasing hydrogen peroxide rather readily.They include types in which hydrogen peroxide is present as a truecrystal hydrate, and types in which hydrogen peroxide is incorporatedcovalently and is released chemically, for example by hydrolysis.Typically, peroxohydrates deliver hydrogen peroxide readily enough thatit can be extracted in measurable amounts into the ether phase of anether/water mixture. Peroxohydrates are characterized in that they failto give the Riesenfeld reaction, in contrast to certain other oxidanttypes described hereinafter. Peroxohydrates are the most common examplesof “hydrogen peroxide source” materials and include the perborates,percarbonates, perphosphates, and persilicates. Other materials whichserve to produce or release hydrogen peroxide are, of course, useful.Mixtures of two or more peroxohydrates can be used, for example when itis desired to exploit differential solubility. Suitable peroxohydratesinclude sodium carbonate peroxyhydrate and equivalent commercial“percarbonate” oxidants, and any of the so-called sodium perboratehydrates, the “tetrahydrate” and “monohydrate” being preferred; thoughsodium pyrophosphate peroxyhydrate can be used. Many such peroxohydratesare available in processed forms with coatings, such as of silicateand/or borate and/or waxy materials and/or surfactants, or have particlegeometries, such as compact spheres, which improve storage stability. Byway of organic peroxohydrates, urea peroxyhydrate can also be usefulherein.

Percarbonate oxidant includes, for example, dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Percarbonates and perborates are widely available in commerce, forexample from FMC, Solvay and Tokai Denka.

Organic percarboxylic acids useful herein as the oxidants includemagnesium monoperoxyphthalate hexahydrate, available from Interox,m-chloro perbenzoic acid and its salts, 4-nonylamino-4-oxoperoxybutyricacid and diperoxydodecanedioic acid and their salts. Such bleaches aredisclosed in U.S. Pat. No. 4,483,781, U.S. patent application Ser. No.740,446, Bums et al, filed Jun. 3, 1985, EP-A 133,354, published Feb.20, 1985, and U.S. Pat. No. 4,412,934. Highly preferred oxidants alsoinclude 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described inU.S. Pat. No. 4,634,551 and include those having formula HO—O—C(O)—R—Ywherein R is an alkylene or substituted alkylene group containing from 1to about 22 carbon atoms or a phenylene or substituted phenylene group,and Y is hydrogen, halogen, alkyl, aryl or —C(O)—OH or —C(O)—O—OH.

Organic percarboxylic acids usable herein include those containing one,two or more peroxy groups and can be aliphatic or aromatic. When theorganic percarboxylic acid is aliphatic, the unsubstituted acid suitablyhas the linear formula: HO—O—C(O)—(CH₂)_(n)-Y where Y can be, forexample, H, CH₃, CH₂Cl, COOH, or C(O)OOH; and n is an integer from 1 to20. Branched analogs are also acceptable. When the organic percarboxylicacid is aromatic, the unsubstituted acid suitably has formula:HO—O—C(O)—C₆H₄—Y wherein Y is hydrogen, alkyl, alkyhalogen, halogen, or—COOH or —C(O)OOH.

Monoperoxycarboxylic acids useful as oxidant herein are furtherillustrated by alkyl percarboxylic acids and aryl percarboxylic acidssuch as peroxybenzoic acid and ring-substituted peroxybenzoic acids,e.g., peroxy-alpha-naphthoic acid; aliphatic, substituted aliphatic andarylalkyl monoperoxy acids such as peroxylauric acid, peroxystearicacid, and N,N-phthaloylaminoperoxycaproic acid (PAP); and6-octylamino-6-oxo-peroxyhexanoic acid. Monoperoxycarboxylic acids canbe hydrophilic, such as peracetic acid, or can be relativelyhydrophobic. The hydrophobic types include those containing a chain ofsix or more carbon atoms, preferred hydrophobic types having a linearaliphatic C8-C14 chain optionally substituted by one or more etheroxygen atoms and/or one or more aromatic moieties positioned such thatthe peracid is an aliphatic peracid. More generally, such optionalsubstitution by ether oxygen atoms and/or aromatic moieties can beapplied to any of the peracids or bleach activators herein.Branched-chain peracid types and aromatic peracids having one or moreC3-C16 linear or branched long-chain substituents can also be useful.The peracids can be used in the acid form or as any suitable salt with ableach-stable cation. Very useful herein are the organic percarboxylicacids of formula:

or mixtures thereof wherein R¹ is alkyl, aryl, or alkaryl containingfrom about 1 to about 14 carbon atoms, R² is alkylene, arylene oralkarylene containing from about 1 to about 14 carbon atoms, and R⁵ is Hor alkyl, aryl, or alkaryl containing from about 1 to about 10 carbonatoms. When these peracids have a sum of carbon atoms in R¹ and R²together of about 6 or higher, preferably from about 8 to about 14, theyare particularly suitable as hydrophobic peracids for bleaching avariety of relatively hydrophobic or “lipophilic” stains, includingso-called “dingy” types. Calcium, magnesium, or substituted ammoniumsalts may also be useful.

Other useful peracids and bleach activators herein are in the family ofimidoperacids and imido bleach activators. These includephthaloylimidoperoxycaproic acid and related arylimido-substituted andacyloxynitrogen derivatives. For listings of such compounds,preparations and their incorporation into laundry compositions includingboth granules and liquids, See U.S. Pat. No. 5,487,818; U.S. Pat. No.5,470,988, U.S. Pat. No. 5,466,825; U.S. Pat. No. 5,419,846; U.S. Pat.No. 5,415,796; U.S. Pat. No. 5,391,324; U.S. Pat. No. 5,328,634; U.S.Pat. No. 5,310,934; U.S. Pat. No. 5,279,757; U.S. Pat. No. 5,246,620;U.S. Pat. No. 5,245,075; U.S. Pat. No. 5,294,362; U.S. Pat. No.5,423,998; U.S. Pat. No. 5,208,340; U.S. Pat. No. 5,132,431 and U.S.Pat. No. 5,087,385.

Useful diperoxyacids include, for example, 1,12-diperoxydodecanedioicacid (DPDA); 1,9-diperoxyazelaic acid; diperoxybrassilic acid;diperoxysebasic acid and diperoxyisophthalic acid;2-decyldiperoxybutane-1,4-dioic acid; and 4,4′-sulphonylbisperoxybenzoicacid. Owing to structures in which two relatively hydrophilic groups aredisposed at the ends of the molecule, diperoxyacids have sometimes beenclassified separately from the hydrophilic and hydrophobic monoperacids,for example as “hydrotropic”: Some of the diperacids are hydrophobic ina quite literal sense, especially when they have a long-chain moietyseparating the peroxyacid moieties.

More generally, the terms “hydrophilic” and “hydrophobic” used herein inconnection with any of the oxidants, especially the peracids, and inconnection with bleach activators, are in the first instance based onwhether a given oxidant effectively performs bleaching of fugitive dyesin solution thereby preventing fabric greying and discoloration and/orremoves more hydrophilic stains such as tea, wine and grape juice—inthis case it is termed “hydrophilic”. When the oxidant or bleachactivator has a significant stain removal, whiteness-improving orcleaning effect on dingy, greasy, carotenoid, or other hydrophobicsoils, it is termed “hydrophobic”. The terms are applicable also whenreferring to peracids or bleach activators used in combination with ahydrogen peroxide source. The current commercial benchmarks forhydrophilic performance of oxidant systems are: TAED or peracetic acid,for benchmarking hydrophilic bleaching. NOBS or NAPAA are thecorresponding benchmarks for hydrophobic bleaching. The terms“hydrophilic”, “hydrophobic” and “hydrotropic” with reference tooxidants including peracids and here extended to bleach activator havealso been used somewhat more narrowly in the literature. See especiallyKirk Othmer's Encyclopedia of Chemical Technology, Vol. 4., pages284-285. This reference provides a chromatographic retention time andcritical micelle concentration-based set of criteria, and is useful toidentify and/or characterize preferred sub-classes of hydrophobic,hydrophilic and hydrotropic oxidants and bleach activators that can beused in the present invention.

Bleach Activators

Bleach activators useful herein include amides, imides, esters andanhydrides. Commonly at least one substituted or unsubstituted acylmoiety is present, covalently connected to a leaving group as in thestructure R—C(O)—L. In one preferred mode of use, bleach activators arecombined with a source of hydrogen peroxide, such as the perborates orpercarbonates, in a single product. Conveniently, the single productleads to in situ production in aqueous solution (i.e., during thewashing process) of the percarboxylic acid corresponding to the bleachactivator. The product itself can be hydrous, for example a powder,provided that water is controlled in amount and mobility such thatstorage stability is acceptable. Alternately, the product can be ananhydrous solid or liquid. In another mode, the bleach activator oroxygen bleach is incorporated in a pretreatment product, such as a stainstick; soiled, pretreated substrates can then be exposed to furthertreatments, for example of a hydrogen peroxide source. With respect tothe above bleach activator structure RC(O)L, the atom in the leavinggroup connecting to the peracid-forming acyl moiety R(C)O— is mosttypically O or N. Bleach activators can have non-charged, positively ornegatively charged peracid-forming moieties and/or noncharged,positively or negatively charged leaving groups. One or moreperacid-forming moieties or leaving-groups can be present. See, forexample, U.S. Pat. No. 5,595,967, U.S. Pat. No. 5,561,235, U.S. Pat. No.5,560,862 or the bis-(peroxy-carbonic) system of U.S. Pat. No.5,534,179. Bleach activators can be substituted with electron-donatingor electron-releasing moieties either in the leaving-group or in theperacid-forming moiety or moieties, changing their reactivity and makingthem more or less suited to particular pH or wash conditions. Forexample, electron-withdrawing groups such as NO₂ improve the efficacy ofbleach activators intended for use in mild-pH (e.g., from about 7.5- toabout 9.5) wash conditions.

Cationic bleach activators include quaternary carbamate-, quaternarycarbonate-, quaternary ester- and quaternary amide-types, delivering arange of cationic peroxyimidic, peroxycarbonic or peroxycarboxylic acidsto the wash. An analogous but non-cationic palette of bleach activatorsis available when quaternary derivatives are not desired. In moredetail, cationic activators include quaternary ammonium-substitutedactivators of WO 96-06915, U.S. Pat. Nos. 4,751,015 and 4,397,757,EP-A-284292, EP-A-331,229 and EP-A-03520 including 2-(N,N,N-trimethylammonium) ethyl-4-sulphophenyl carbonate-(SPCC); N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride-(ODC); 3-(N,N,N-trimethylammonium) propyl sodium-4-sulphophenyl carboxylate; and N,N,N-trimethylammonium toluyloxy benzene sulfonate. Also useful are cationic nitritesas disclosed in EP-A-303,520 and in European Patent Specification458,396 and 464,880. Other nitrile types have electron-withdrawingsubstituents as described in U.S. Pat. No. 5,591,378; examples including3,5-dimethoxybenzonitrile and 3,5-dinitrobenzonitrile.

Other bleach activator disclosures include GB 836,988; 864,798; 907,356;1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522;EP-A-0174132; EP-A-0120591; U.S. Pat. Nos. 1,246,339; 3,332,882;4,128,494; 4,412,934 and 4,675,393, and the phenol sulfonate ester ofalkanoyl aminoacids disclosed in U.S. Pat. No. 5,523,434. Suitablebleach activators include any acetylated diamine types, whetherhydrophilic or hydrophobic in character.

Of the above classes of bleach precursors, preferred classes include theesters, including acyl phenol sulfonates, acyl alkyl phenol sulfonatesor acyl oxybenzenesulfonates (OBS leaving-group); the acyl-amides; andthe quaternary ammonium substituted peroxyacid precursors including thecationic nitrites.

Preferred bleach activators include N,N,N′N′-tetraacetyl ethylenediamine (TAED) or any of its close relatives including the triacetyl orother unsymmetrical derivatives. TAED and the acetylated carbohydratessuch as glucose pentaacetate and tetraacetyl xylose are preferredhydrophilic bleach activators. Depending on the application, acetyltriethyl citrate, a liquid, also has some utility, as does phenylbenzoate.

Preferred hydrophobic bleach activators include sodiumnonanoyloxybenzene sulfonate (NOBS or SNOBS), substituted amide typesdescribed in detail hereinafter, such as activators related to NAPAA,and activators related to certain imidoperacid bleaches, for example asdescribed in U.S. Pat. No. 5,061,807, issued Oct. 29, 1991 and assignedto Hoechst Aktiengesellschaft of Frankfurt, Germany. Japanese Laid-OpenPatent Application (Kokai) No. 4-28799 for example describes a bleachingagent and a bleaching detergent composition comprising an organicperacid precursor described by a general formula and illustrated bycompounds which may be summarized more particularly as conforming to theformula:

wherein L is sodium p-phenolsulfonate, R¹ is CH₃ or C₁₂H₂₅ and R² is H.Analogs of these compounds having any of the leaving-groups identifiedherein and/or having R1 being linear or branched C6-C16 are also useful.

Another group of peracids and bleach activators herein are thosederivable from acyclic imidoperoxycarboxylic acids and salts thereof ofthe formula:

cyclic imidoperoxycarboxylic acids and salts thereof of the formula

and (iii) mixtures of saidcompounds, (i) and (ii);wherein M is selected from hydrogen and bleach-compatible cations havingcharge q; and y and z are integers such that said compound iselectrically neutral; E, A and X comprise hydrocarbyl groups; and saidterminal hydrocarbyl groups are contained within E and A. The structureof the corresponding bleach activators is obtained by deleting theperoxy moiety and the metal and replacing it with a leaving-group L,which can be any of the leaving-group moieties defined elsewhere herein.In preferred embodiments, there are encompassed detergent compositionswherein, in any of said compounds, X is linear C3-C8 alkyl; A isselected from:

wherein n is from 0 to about 4, and

wherein R¹ and E are said terminal hydrocarbyl groups, R², R³ and R⁴ areindependently selected from H, C₁-C₃ saturated alkyl, and C₁-C₃unsaturated alkyl; and wherein said terminal hydrocarbyl groups arealkyl groups comprising at least six carbon atoms, more typically linearor branched alkyl having from about 8 to about 16 carbon atoms.

Other suitable bleach activators include sodium-4-benzoyloxy benzenesulfonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate;sodium-4-methyl-3-benzoyloxy benzoate (SPCC); trimethyl ammoniumtoluyloxy-benzene sulfonate; or sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (STHOBS).

Bleach activators may be used in an amount of up to 20%, preferably from0.1-10% by weight, of the composition, though higher levels, 40% ormore, are acceptable, for example in highly concentrated bleach additiveproduct forms or forms intended for appliance automated dosing.

Highly preferred bleach activators useful herein are amide-substitutedand have either of the formulae:

or mixtures thereof, wherein R¹ is alkyl, aryl, or alkaryl containingfrom about 1 to about 14 carbon atoms including both hydrophilic types(short R¹) and hydrophobic types (R¹ is especially from about 8 to about12), R² is alkylene, arylene or alkarylene containing from about 1 toabout 14 carbon atoms, R⁵ is H, or an alkyl, aryl, or alkaryl containingfrom about 1 to about 10 carbon atoms, and L is a leaving group.

A leaving group as defined herein is any group that is displaced fromthe bleach activator as a consequence of attack by perhydroxide orequivalent reagent capable of liberating a more potent bleach from thereaction. Perhydrolysis is a term used to describe such reaction. Thusbleach activators perhydrolyze to liberate peracid. Leaving groups ofbleach activators for relatively low-pH washing are suitablyelectron-withdrawing. Preferred leaving groups have slow rates ofreassociation with the moiety from which they have been displaced.Leaving groups of bleach activators are preferably selected such thattheir removal and peracid formation are at rates consistent with thedesired application, e.g., a wash cycle. In practice, a balance isstruck such that leaving-groups are not appreciably liberated, and thecorresponding activators do not appreciably hydrolyze or perhydrolyze,while stored in a bleaching composition. The pK of the conjugate acid ofthe leaving group is a measure of suitability, and is typically fromabout 4 to about 16, preferably from about 6 to about 12, morepreferably from about 8 to about 11.

Preferred bleach activators include those of the formulae, for examplethe amide-substituted formulae, hereinabove, wherein R¹,R² and R⁵ are asdefined for the corresponding peroxyacid and L is selected from thegroup consisting of:

and mixtures thereof, wherein R¹ is a linear or branched alkyl, aryl, oralkaryl group containing from about 1 to about 14 carbon atoms, R³ is analkyl chain containing from 1 to about 8 carbon atoms, R⁴ is H or R³,and Y is H or a solubilizing group. These and other known leaving groupsare, more generally, general suitable alternatives for introduction intoany bleach activator herein. Preferred solubilizing groups include—SO3⁻M⁺, —CO2⁻M⁺, —SO4⁻M⁺, —N⁺(R)4X⁻ and O←N(R³)2, more preferably—SO3⁻M⁺ and —CO2⁻M⁺ wherein R3 is an alkyl chain containing from about 1to about 4 carbon atoms, M is a bleach-stable cation and X is ableach-stable anion, each of which is selected consistent withmaintaining solubility of the activator. Under some circumstances, forexample solid-form European heavy-duty granular detergents, any of theabove bleach activators are preferably solids having crystallinecharacter and melting-point above about 50 deg. C; in these cases,branched alkyl groups are preferably not included in the oxygen bleachor bleach activator; in other formulation contexts, for exampleheavy-duty liquids with bleach or liquid bleach additives, low-meltingor liquid bleach activators are preferred. Melting-point reduction canbe favored by incorporating branched, rather than linear alkyl moietiesinto the oxygen bleach or precursor.

When solubilizing groups are added to the leaving group, the activatorcan have good water-solubility or dispersibility while still beingcapable of delivering a relatively hydrophobic peracid. Preferably, M isalkali metal, ammonium or substituted ammonium, more preferably Na or K,and X is halide, hydroxide, methylsulfate or acetate. Solubilizinggroups can, more generally, be used in any bleach activator herein.Bleach activators of lower solubility, for example those with leavinggroup not having a solubilizing group, may need to be finely divided ordispersed in bleaching solutions for acceptable results.

Preferred bleach activators also include those of the above generalformula wherein L is selected from the group consisting of:

wherein R³ is as defined above and Y is —SO3⁻M⁺ or —CO2⁻M⁺ wherein M isas defined above.

Preferred examples of bleach activators of the above formulae include(6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, andmixtures thereof.

Other useful activators, disclosed in U.S. Pat. No. 4,966,723, arebenzoxazin-type, such as a C₆H₄ ring to which is fused in the1,2-positions a moiety —C(O)OC(R¹)═N—.

Depending on the activator and precise application, good bleachingresults can be obtained from bleaching systems having with in-use pH offrom about 6 to about 13, preferably from about 9.0 to about 10.5.Typically, for example, activators with electron-withdrawing moietiesare used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

Acyl lactam activators are very useful herein, especially the acylcaprolactams (see for example WO 94-28102 A) and acyl valerolactams (seeU.S. Pat. No. 5,503,639) of the formulae:

wherein R⁶ is H, alkyl, aryl, alkoxyaryl, an alkaryl group containingfrom 1 to about 12 carbon atoms, or substituted phenyl containing fromabout 6 to about 18 carbons. See also U.S. Pat. No. 4,545,784 whichdiscloses acyl caprolactams, including benzoyl caprolactam adsorbed intosodium perborate. In certain preferred embodiments of the invention,NOBS, lactam activators, imide activators or amide-functionalactivators, especially the more hydrophobic derivatives, are desirablycombined with hydrophilic activators such as TAED, typically at weightratios of hydrophobic activator: TAED in the range of 1:5 to 5:1,preferably about 1:1. Other suitable lactam activators arealpha-modified, see WO 96-22350 A1, Jul. 25, 1996. Lactam activators,especially the more hydrophobic types, are desirably used in combinationwith TAED, typically at weight ratios of amido-derived or caprolactamactivators: TAED in the range of 1:5 to 5:1, preferably about 1:1. Seealso the bleach activators having cyclic amidine leaving-group disclosedin U.S. Pat. No. 5,552,556.

Nonlimiting examples of additional activators useful herein are to befound in U.S. Pat. No. 4,915,854, U.S. Pat. Nos. 4,412,934 and4,634,551. The hydrophobic activator nonanoyloxybenzene sulfonate (NOBS)and the hydrophilic tetraacetyl ethylene diamine (TAED) activator aretypical, and mixtures thereof can also be used.

The superior bleaching/cleaning action of the present compositions isalso preferably achieved with safety to natural rubber machine parts,for example of certain european washing appliances (see WO 94-28104) andother natural rubber articles, including fabrics containing naturalrubber and natural rubber elastic materials. Complexities of bleachingmechanisms are legion and are not completely understood.

Additional activators useful herein include those of U.S. Pat. No.5,545,349. Examples include esters of an organic acid and ethyleneglycol, diethylene glycol or glycerin, or the acid imide of an organicacid and ethylenediamine; wherein the organic acid is selected frommethoxyacetic acid, 2-methoxypropionic acid, p-methoxybenzoic acid,ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid,propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic acid,butoxyacetic acid, 2-butoxypropionic acid, p-butoxybenzoic acid,2-methoxyethoxyacetic acid,2-methoxy-1-methylethoxyacetic acid,2-methoxy-2-methylethoxyacetic acid,2-ethoxyethoxyacetic acid,2-(2-ethoxyethoxy)propionic acid, p-(2-ethoxyethoxy)benzoic acid,2-ethoxy-1-methylethoxyacetic acid, 2-ethoxy-2-methylethoxyacetic acid,2-propoxyethoxyacetic acid, 2-propoxy-1-methylethoxyaceticacid,2-propoxy-2-methylethoxyacetic acid, 2-butoxyethoxyacetic acid,2-butoxy-1-methylethoxyacetic acid, 2-butoxy-2-methylethoxyacetic acid,2-(2-methoxyethoxy)ethoxyacetic acid,2-(2-methoxy-1-methylethoxy)ethoxyacetic acid,2-(2-methoxy-2-methylethoxy)ethoxyacetic acid and2-(2-ethoxyethoxy)ethoxyacetic acid.

Enzymatic sources of hydrogen peroxide

On a different track from the bleach activators illustrated hereinabove,another suitable hydrogen peroxide generating system is a combination ofa C₁-C₄ alkanol oxidase and a C₁-C₄ alkanol, especially a combination ofmethanol oxidase (MOX) and ethanol. Such combinations are disclosed inWO 94/03003. Other enzymatic materials related to bleaching, such asperoxidases, haloperoxidases, oxidases, superoxide dismutases, catalasesand their enhancers or, more commonly, inhibitors, may be used asoptional ingredients in the instant compositions.

Oxygen transfer agents and precursors

Also useful herein are any of the known organic bleach catalysts, oxygentransfer agents or precursors therefor. These include the compoundsthemselves and/or their precursors, for example any suitable ketone forproduction of dioxiranes and/or any of the hetero-atom containinganalogs of dioxirane precursors or dioxiranes, such as sulfoniminesR¹R²C═NSO₂R³, see EP 446 982 A, published 1991 and sulfonyloxaziridines,for example:

see EP 446,981 A, published 1991. Preferred examples of such materialsinclude hydrophilic or hydrophobic ketones, used especially inconjunction with monoperoxysulfates to produce dioxiranes in situ,and/or the imines described in U.S. Pat. No. 5,576,282 and referencesdescribed therein. Oxygen bleaches preferably used in conjunction withsuch oxygen transfer agents or precursors include percarboxylic acidsand salts, percarbonic acids and salts, peroxymonosulfuric acid andsalts, and mixtures thereof. See also U.S. Pat. No. 5,360,568; U.S. Pat.No. 5,360,569; and U.S. Pat. No. 5,370,826.

Catalytic System Combinations

While the combinations of ingredients used with the transition-metalbleach catalysts of the invention can be widely permuted, someparticularly preferred combinations include:

(a) transition metal bleach catalyst +hydrogen peroxide source alone,e.g., sodium perborate or percarbonate;

(b) as (a) but with the further addition of a bleach activator selectedfrom

-   -   (i) hydrophilic bleach activators;    -   (ii) hydrophobic bleach activators and    -   (iii) mixtures thereof;

(c) transition metal bleach catalyst +peracid alone, e.g.,

-   -   (i) hydrophilic peracid, e.g., peracetic acid;    -   (ii) hydrophobic peracid, e.g., NAPAA or peroxylauric acid;    -   (iii) inorganic peracid, e.g., peroxymonosulfuric acid K salts;

(d) use (a), (b) or (c) with the further addition of an oxygen transferagent or precursor therefor; especially (c) +oxygen transfer agent.

Any of (a)-(d) can be further combined with one or more polymericdispersants, sequestrants, antioxidants, fluorescent whitening agents,photobleaches and/or dye transfer inhibitors. In such combinations, thetransition metal bleach catalyst will preferably be at levels in a rangesuited to provide wash (in-use) concentrations of from about 0.1 toabout 10 ppm (weight of catalyst); the other components being used attheir known levels which may vary widely.

While there is currently no certain advantage, the transition metalcatalysts of the invention can be used in combination withheretofore-disclosed transition metal bleach or dye transfer inhibitioncatalysts, such as the Mn or Fe complexes of triazacyclononanes, the Fecomplexes of N,N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine(U.S. Pat. No. 5,580,485) and the like. For example, when the transitionmetal bleach catalyst is one disclosed to be particularly effective forsolution bleaching and dye transfer inhibition, as is the case forexample with certain transition metal complexes of porphyrins, it may becombined with one better suited for promoting interfacial bleaching ofsoiled substrates.

Laundry and Cleaning Compositions and Methods:

In general, a laundry or cleaning adjunct is any material required totransform a composition containing only transition-metal bleach catalystinto a composition useful for laundry or cleaning purposes. Adjuncts ingeneral include detersive surfactants, builders, enzymes, and likematerials having an independent cleaning function; and also stabilizers,diluents, structuring materials, agents having aesthetic effect such ascolorants, pro-perfumes and perfumes. In preferred embodiments, laundryor cleaning adjuncts are readily recognizable to those of skill in theart as being characteristic of laundry or cleaning products, especiallyof laundry or cleaning products intended for direct use by a consumer ina domestic environment.

In a hard surface cleaning or fabric laundering operation which uses thepresent invention catalytic systems, the target substrate will typicallybe a fabric or surface stained with, for example, various food stains.

In the case of use in laundry or hard surface catalytic systems ormethods, the catalytically effective amount of transition-metaloxidation catalyst is that sufficient to enhance the appearance of asoiled surface. In such cases, the appearance is typically improved inone or more of whiteness, brightness and de-staining; and acatalytically effective amount is one requiring less than astoichiometric number of moles of catalyst when compared with the numberof moles of primary oxidant, such as hydrogen peroxide or hydrophobicperacid, required to produce measurable effect. In addition to directobservation of the bulk surface being bleached or cleaned, catalyticbleaching effect can (where appropriate) be measured indirectly, such asby measurement of the kinetics or end-result of oxidizing a dye insolution.

By “effective amount” in a laundry or cleaning adjunct context is meantan amount of a material, such as a detergent adjunct, which issufficient under whatever comparative or use conditions are employed, toprovide the desired end-result benefit, for example in laundry andcleaning methods to improve the appearance of a soiled surface in one ormore use cycles. A “use cycle” is, for example, one wash of a bundle offabrics by a consumer. Appearance or visual effect can be measured bythe consumer, by technical observers such as trained panelists, or bytechnical instrument means such as spectroscopy or image analysis.

Unless otherwise indicated, the detergent or detergent additivecompositions may be formulated as granular or power-form all-purpose or“heavy-duty” washing agents, especially laundry detergents; liquid, gelor paste-form all-purpose washing agents, especially the so-calledheavy-duty liquid types; liquid fine-fabric detergents; hand dishwashingagents or light duty dishwashing agents, especially those of thehigh-foaming type; machine dishwashing agents, including the varioustabletted, granular, liquid and rinse-aid types for household andinstitutional use; liquid cleaning and disinfecting agents, includingantibacterial hand-wash types, laundry bars, mouthwashes, denturecleaners, car or carpet shampoos, bathroom cleaners; hair shampoos andhair-rinses; shower gels and foam baths and metal cleaners; as well ascleaning auxiliaries such as bleach additives and “stain-stick” orpre-treat types.

Catalytic systems herein as incorporated into detergents can includeboron-free, phosphate-free, or chlorine-free embodiments.

Desirable adjuncts more generally include detersive surfactants,builders, enzymes, dispersant polymers, color speckles, silvercare,anti-tarnish and/or anti-corrosion agents, dyes, fillers, germicides,alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizingagents, perfumes, solubilizing agents, carriers, processing aids,pigments, and, for liquid formulations, solvents, as described in detailhereinafter.

Quite typically, laundry or cleaning compositions herein such as laundrydetergents, laundry detergent additives, hard surface cleaners,automatic dishwashing detergents, synthetic and soap-based laundry bars,fabric softeners and fabric treatment liquids, solids and treatmentarticles of all kinds will require several adjuncts, though certainsimply formulated products, such as bleach additives, may require onlymetal catalyst and a single supporting material such as a detergentbuilder or surfactant which helps to make the potent catalyst availableto the consumer in a manageable dose.

Catalyst system compositions of the present invention useful for laundryor cleaning products comprise transition-metal bleach catalystcomprising a complex of a transition metal and a macropolycyclic rigidligand as defined herein. The compositions also comprise at least oneadjunct material, preferably comprising an oxygen bleaching agent suchas a source of hydrogen peroxide. More preferably, the adjunct componentincludes both an oxygen bleaching agent and at least one other adjunctmaterial selected from non-bleaching adjuncts suited for laundrydetergents or cleaning products. Non-bleaching adjuncts as definedherein are adjuncts useful in detergents and cleaning products whichneither bleach on their own, nor are recognized as adjuncts used incleaning primarily as promoters of bleaching such as is the case withbleach activators, organic bleach catalysts or peracids. Preferrednon-bleaching adjuncts include detersive surfactants, detergentbuilders, non-bleaching enzymes having a useful function in detergents,and the like. Preferred cleaning compositions herein can incorporate asource of hydrogen peroxide which is any common hydrogen-peroxidereleasing salt, such as sodium perborate, sodium percarbonate, andmixtures thereof. Also useful are other sources of available oxygen suchas persulfate (e.g., OXONE, manufactured by DuPont), as well aspreformed organic peracids.

In a hard surface cleaning or fabric laundering operation which uses thepresent invention compositions, the target substrate, that is, thematerial to be cleaned, will typically be a fabric or surface stainedwith, for example, various hydrophilic food stains, such as coffee, teaor wine; with hydrophobic stains such as greasy or carotenoid stains; oris a “dingy” surface, for example one yellowed by the presence of arelatively uniformly distributed fine residue of hydrophobic soils.

In the preferred laundry compositions, adjuncts such as buildersincluding zeolites and phosphates, surfactants such as anionic and/ornonionic and/or cationic surfactants, dispersant polymers (which modifyand inhibit crystal growth of calcium and/or magnesium salts), chelants(which control wash water introduced transition metals), alkalis (toadjust pH), and detersive enzymes are present. Additionalbleach-modifying adjuncts such as conventional bleach activators such asTAED and/or NOBS may be added, provided that any such materials aredelivered in such a manner as to be compatible with the purposes of thepresent invention. The present detergent or detergent-additivecompositions may, moreover, comprise one or more processing aids,fillers, perfumes, conventional enzyme particle-making materialsincluding enzyme cores or “nonpareils”, as well as pigments, and thelike. In the preferred laundry compositions, additional ingredients suchas soil release polymers, brighteners, and/or dye transfer inhibitorscan be present.

The inventive compositions can include laundry detergents, hard-surfacecleaners and the like which include all the components needed forcleaning; alternatively, the compositions can be made for use ascleaning additives. A cleaning additive, for example, can be acomposition containing the transition-metal bleach catalyst, a detersivesurfactant, and a builder, and can be sold for use as an “add-on”, to beused with a conventional detergent which contains a perborate,percarbonate, or other primary oxidant. The compositions herein caninclude automatic dishwashing compositions (ADD) and denture cleaners,thus, they are not, in general, limited to fabric washing.

In general, adjunct materials used for the production of ADDcompositions herein are preferably checked for compatibility withspotting/filming on glassware. Test methods for spotting/filming aregenerally described in the automatic dishwashing detergent literature,including DIN test methods. Certain oily materials, especially thosehaving longer hydrocarbon chain lengths, and insoluble materials such asclays, as well as long-chain fatty acids or soaps which form soap scumare therefore preferably limited or excluded from such compositions.

Amounts of the essential ingredients can vary within wide ranges,however preferred cleaning compositions herein (which have a 1% aqueoussolution pH of from about 6 to about 13, more preferably from about 7.5to about 11.5, and most preferably less than about 11, especially fromabout 9 to about 10.5) are those wherein there is present: from about0.01 ppm to about 500 ppm of a transition-metal bleach catalyst inaccordance with the invention, and the balance, typically from at leastabout 90% to about 100% of one or more laundry or cleaning adjuncts. Inpreferred embodiments, there can be present (also expressed as apercentage by weight of the entire composition) from 0.1% to about 90%,preferably from about 0.5% to about 50% of a primary oxidant, such as apreformed peracid or a source of hydrogen peroxide; from 0% to about20%, preferably at least about 0.001%, of a conventionalbleach-promoting adjunct, such as a hydrophilic bleach activator, ahydrophobic bleach activator, or a mixture of hydrophilic andhydrophobic bleach activators, and at least about 0.001%, preferablyfrom about 1% to about 40%, of a laundry or cleaning adjunct which doesnot have a primary role in bleaching, such as a detersive surfactant, adetergent builder, a detergent enzyme, a stabilizer, a detergent buffer,or mixtures thereof. Such fully-formulated embodiments desirablycomprise, by way of non-bleaching adjuncts, from about 0.1% to about 15%of a polymeric dispersant, from about 0.01% to about 10% of a chelant,and from about 0.00001% to about 10% of a detersive enzyme thoughfurther additional or adjunct ingredients, especially colorants,perfumes, pro-perfumes (compounds which release a fragrance whentriggered by any suitable trigger such as heat, enzyme action, or changein pH) may be present. Preferred adjuncts herein are selected frombleach-stable types, though bleach-unstable types can often be includedthrough the skill of the formulator.

Detergent compositions herein can have any desired physical form; whenin granular form, it is typical to limit water content, for example toless than about 10%, preferably less than about 7% free water, for beststorage stability. However, liquid forms using both aqueous and/ornonaqueous solvents are also included.

Further, preferred compositions of this invention include those whichare substantially free of chlorine bleach. By “substantially free” ofchlorine bleach is meant that the formulator does not deliberately add achlorine-containing bleach additive, such as hypochlorite or a sourcethereof, such as a chlorinated isocyanurate, to the preferredcomposition. However, it is recognized that because of factors outsidethe control of the formulator, such as chlorination of the water supply,some non-zero amount of chlorine bleach may be present in the washliquor. The term “substantially free” can be similarly constructed withreference to preferred limitation of other ingredients, such asphosphate builder.

In a fabric laundering operation, the target substrate will typically bea fabric stained with, for example, various food stains. The testconditions will vary, depending on the type of washing appliance usedand the habits of the user. Thus, front-loading laundry washing machinesof the type employed in Europe generally use less water and higherdetergent concentrations than do top-loading U.S.-style machines. Somemachines have considerably longer wash cycles than others. Some userselect to use very hot water; others use warm or even cold water infabric laundering operations. Of course, the catalytic performance ofthe transition-metal bleach catalyst will be affected by suchconsiderations, and the levels of transition-metal bleach catalyst usedin fully-formulated detergent and bleach compositions can beappropriately adjusted. As a practical matter, and not by way oflimitation, the compositions and processes herein can be adjusted toprovide on the order of at least one part per ten million of the activetransition-metal bleach catalyst, in the aqueous washing liquor, andwill preferably provide from about 0.01 ppm to about 1.0 ppm, morepreferably from about 0.03 ppm to about 0.6 ppm, of the transition-metalbleach catalyst, in the laundry liquor. To illustrate this pointfurther, on the order of 3 micromolar transition-metal bleach catalystis effective at 40° C., pH 10 under European conditions using perborateand a bleach activator (e.g., nonanoyloxybenzenesulfonate). An increasein concentration of 3-5 fold may be required under U.S. conditions toachieve the same results. Conversely, use of a bleach activator and thetransition-metal bleach catalyst with perborate may allow the formulatorto achieve equivalent bleaching at lower perborate usage levels thanproducts without the transition-metal bleach catalyst.

The bulk density of granular detergent compositions in accordance withthe present invention typically have a bulk density of at least 600g/liter, more preferably from 650 g/liter to 1200 g/liter. Bulk densityis measured by means of a simple funnel and cup device consisting of aconical funnel molded rigidly on a base and provided with a flap valveat its lower extremity to allow the contents of the funnel to be emptiedinto an axially aligned cylindrical cup disposed below the funnel. Thefunnel is 130 mm high and has internal diameters of 130 mm and 40 mm atits respective upper and lower extremities. It is mounted so that thelower extremity is 140 mm above the upper surface of the base. The cuphas an overall height of 90 mm, an internal height of 87 mm and aninternal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by handpouring, the flap valve is opened and powder allowed to overfill thecup. The filled cup is removed from the frame and excess powder removedfrom the cup by passing a straight edged implement e.g.; a knife, acrossits upper edge. The filled cup is then weighed and the value obtainedfor the weight of powder doubled to provide a bulk density in g/liter.Replicate measurements are made as required.

The instant compositions may include a detersive surfactant as apreferred component. Detersive surfactants are extensively illustratedin U.S. Pat. No. 3,929,678, Dec. 30, 1975 Laughlin, et al, and U.S. Pat.No. 4,259,217, Mar. 31, 1981, Murphy; in the series “SurfactantScience”, Marcel Dekker, Inc., New York and Basel; in “Handbook ofSurfactants”, M. R. Porter, Chapman and Hall, 2nd Ed., 1994; in“Surfactants in Consumer Products”, Ed. J. Falbe, Springer-Verlag, 1987;and in numerous detergent-related patents assigned to Procter & Gambleand other detergent and consumer product manufacturers. The preferreddetersive surfactant herein therefore includes anionic, nonionic,zwitterionic or amphoteric types of surfactant known for use as cleaningagents in textile laundering. Detersive surfactants useful herein aretypically present at levels from 1% to 55%, by weight.

Preferred detersive surfactants are: acid, sodium and ammonium C9-C20alkylbenzenesulfonates, particularly sodium linear secondary alkylC₁₀-C15 benzenesulfonates (1), including straight-chain and branchedforms; olefinsulfonate salts, (2), that is, material made by reactingolefins, particularly C₁₀-C₂₀ α-olefins, with sulfur trioxide and thenneutralizing and hydrolyzing the reaction product; sodium and ammoniumC₇-C₁₂ dialkyl sulfosuccinates, (3); alkane monosulfonates, (4), such asthose derived by reacting C₈-C₂₀ α-olefins with sodium bisulfite andthose derived by reacting paraffins with SO₂ and Cl₂ and thenhydrolyzing with a base to form a random sulfonate; α-Sulfo fatty acidsalts or esters, (10); sodium alkylglycerylsulfonates, (11), especiallythose ethers of the higher alcohols derived from tallow or coconut oiland synthetic alcohols derived from petroleum; alkyl or alkenylsulfates, (15), which may be primary or secondary, saturated orunsaturated, branched or unbranched. Such compounds when branched can berandom or regular. When secondary, they preferably have formulaCH₃(CH₂)_(x)(CHOSO₃ ⁻M⁺) CH₃ or CH₃(CH₂)_(y)(CHOSO₃ ⁻M⁺) CH₂CH₃ where xand (y+1) are integers of at least 7, preferably at least 9 and M is awater-soluble cation, preferably sodium. When unsaturated, sulfates suchas oleyl sulfate are preferred, while the sodium and ammonium alkylsulfates, especially those produced by sulfating C₈-C₁₈ alcohols,produced for example from tallow or coconut oil are also useful; alsopreferred are the alkyl or alkenyl ether sulfates, (16), especially theethoxy sulphates having about 0.5 moles or higher of ethoxylation,preferably from 0.5-8; the alkylethercarboxylates, (19), especially theEO 1-5 ethoxycarboxylates; soaps or fatty acids (21), preferably themore water-soluble types; aminoacid-type surfactants, (23), such assarcosinates, especially oleyl sarcosinate; phosphate esters, (26);alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, (30),especially the ethoxylates “AE”, including the so-called narrow peakedalkyl ethoxylates and C₆-C₁₂ alkyl phenol alkoxylates as well as theproducts of aliphatic primary or secondary linear or branched C₈-C₁₈alcohols with ethylene oxide, generally 2-30 EO; N-alkyl polyhydroxyfatty acid amides especially the C₁₂-C₁₈ N-methylglucamides, (32), seeWO 9206154, and N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈N-(3-methoxypropyl) glucamide while N-propyl through N-hexyl C₁₂-C₁₈glucamides can be used for low sudsing; alkyl polyglycosides, (33);amine oxides, (40), preferably alkyldimethylamine N-oxides and theirdihydrates; sulfobetaines or “sultaines”, (43); betaines (44); andgemini surfactants.

Preferred levels of anionic detersive surfactants herein are in therange from about 3% to about 30% or higher, preferably from about 8% toabout 20%, more preferably still, from about 9% to about 18% by weightof the detergent composition. Preferred levels of nonionic detersivesurfactant herein are from about 1% to about 20%, preferably from about3% to about 18%, more preferably from about 5% to about 15%. Desirableweight ratios of anionic: nonionic surfactants in combination includefrom 1.0:9.0 to 1.0:0.25, preferably 1.0:1.5 to 1.0:0.4. Preferredlevels of cationic detersive surfactant herein are from about 0.1% toabout 10%, preferably from about 1% to about 3.5%, although much higherlevels, e.g., up to about 20% or more, may be useful especially innonionic:cationic (i.e., limited or anionic-free) formulations.Amphoteric or zwitterionic detersive surfactants when present areusually useful at levels in the range from about 0.1% to about 20% byweight of the detergent composition. Often levels will be limited toabout 5% or less, especially when the amphoteric is costly.

The surfactant system herein is preferably present in granularcompositions in the form of surfactant agglomerate particles, which maytake the form of flakes, prills, marumes, noodles, ribbons, butpreferably take the form of granules. The most preferred way to processthe particles is by agglomerating powders (e.g. aluminosilicate,carbonate) with high active surfactant pastes and to control theparticle size of the resultant agglomerates within specified limits.Such a process involves mixing an effective amount of powder with a highactive surfactant paste in one or more agglomerators such as a panagglomerator, a Z-blade mixer or more preferably an in-line mixer suchas those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS,Lelystad, Netherlands, and Gebruder Lödige Maschinenbau GmbH, D-4790Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferablya high shear mixer is used, such as a Lödige CB (Trade Name).

A high active surfactant paste comprising from 50% by weight to 95% byweight, preferably 70% by weight to 85% by weight of surfactant istypically used. The paste may be pumped into the agglomerator at atemperature high enough to maintain a pumpable viscosity, but low enoughto avoid degradation of the anionic surfactants used. An operatingtemperature of the paste of 50° C. to 80° C. is typical.

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is meant from 40 g to 300 g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65liters, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

As noted, the surfactants are used herein at levels which are effectivefor achieving at least a directional improvement in cleaningperformance. In the context of a fabric laundry composition, such “usagelevels” can vary depending not only on the type and severity of thesoils and stains, but also on the wash water temperature, the volume ofwash water and the type of washing machine.

Any suitable methods for machine washing or cleaning soiled tableware,particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof, with an aqueous liquid having dissolved ordispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from 8 g to 60 g of productdissolved or dispersed in a wash solution of volume from 3 to 10 liters,as are typical product dosages and wash solution volumes commonlyemployed in conventional machine dishwashing methods.

EXAMPLE 13

Dichloro Manganese (II)

5,8 Dimethyl-1,5,8,12-tetraazabicyclo[ 10.3.2]heptadecane Synthesis

Synthesis of 1,5,9,13-Tetraazatetracyclo[11.2.2.2^(5,9)]heptadecane

1,4,8,12-tetraazacyclopentadecane (4.00 g, 18.7 mmol) is suspended inacetonitrile (30 mL) under nitrogen and to this is added glyoxal (3.00g, 40% aqueous, 20.7 mmol). The resulting mixture is heated at 65° C.for 2 hours. The acetonitrile is removed under reduced pressure.Distilled water (5 mL) is added and the product is extracted withchloroform (5×40 mL). After drying over anhydrous sodium sulfate andfiltration, the solvent is removed under reduced pressure. The productis then chromatographed on neutral alumina (15×2.5 cm) usingchloroform/methanol (97.5:2.5 increasing to 95:5). The solvent isremoved under reduced pressure and the resulting oil is dried undervacuum, overnight. Yield: 3.80 g, 1 (87%).

Synthesis of1,13-Dimethyl-1,13-diazonia-5,9-diazatetracyclo[11.2.2.2^(5,9)]heptadecanediiodide

1,5,9,13-tetraazatetracyclo[11.2.2.2^(5,9)]heptadecane (5.50 g, 23.3mmol) is dissolved in acetonitrile (180 mL) under nitrogen. Iodomethane(21.75 mL, 349.5 mmol) is added and the reaction is stirred at RT for 10days. The solution is rotovapped down to a dark brown oil. The oil istaken up in absolute ethanol (100 mL) and this solution is refluxed 1hour. During that time, a tan solid formed which is separated from themother liquor by vacuum filtration using Whatman #1 filter paper. Thesolid is dried under vacuum, overnight. Yield: 1.79 g, II, (15%). FabMass Spec. TG/G, MeOH) M⁺266 mu, 60%, MI⁺393 mu, 25%.

Synthesis of 5,8 Dimethyl-1,5,8,12-tetraazabicyclo[ 10.3.2]heptadecaneTo a stirred solution of II, (1.78 g, 3.40 mmol) in ethanol (100 mL,95%)is added sodium borohydride (3.78 g. 0.100 mmol). The reaction isstirred under nitrogen at RT for 4 days. 10% Hydrochloric acid is slowlyadded until the pH is 1-2 to decompose the unreacted NaBH₄. Ethanol (70mL) is then added. The solvent is removed by roto-evaporation underreduced pressure. The product is then dissolved in aqueous KOH (125 mL,20%), resulting in a pH 14 solution. The product is then extracted withbenzene (5×60 mL) and the combined organic layers are dried overanhydrous sodium sulfate. After filtering, the solvent is removed underreduced pressure. The residue is slurried with crushed KOH and thendistilled at 97° C. at ˜1 mm pressure. Yield: 0.42 g, III, 47%. MassSpec. (D-CI/NH₃/CH₂Cl₂) MH⁺, 269 mu, 100%.

Synthesis of Dichloro Manganese (II) 5,8Dimethyl-1,5,8,12-tetraazabicyclo[10.3.2]heptadecane

The ligand III, (0.200 g, 0.750 mmol) is dissolved in acetonitrile (4.0mL) and is added to maganese(II) dipyridine dichloride (0.213 g, 0.75mmol). The reaction is stirred for four hours at RT to yield a pale goldsolution. The solvent is removed under reduced pressure. Sodiumthiocyanate (0.162 g, 2.00 mmol) dissolved in methanol (4 mL) is thenadded. The reaction is heated 15 minutes. The reaction solution is thenfiltered through celite and allowed to evaporate. The resulting crystalsare washed with ethanol and dried under vacuum. Yield: 0.125 g, 38%.This solid contains NaCl so it is recrystallized in acetonitrile toyield 0.11 g off a white solid. Elemental analysis theoretical: % C,46.45, % H, 7.34,% N, 19.13. Found: % C, 45.70, % H, 7.10, % N, 19.00.

1. A metal complex comprising: (A) a transition metal atom selected fromthe group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III),Fe(IV), Co(I), Co(II), Co(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI),V(Ell), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II),Ru(II), Ru(III), and Ru(IV); and (B) a cross-bridged macropolycyclicligand comprising; (1) an organic macrocycle ring that comprises atleast 4 donor atoms, 2 of said donor atoms being non-adjacent donoratoms; and (2) a moiety that comprises a cross-bridged chain thatcovalently connects at least 2 non-adjacent donor atoms of said organicmacrocycle ring, said covalently connected donor atoms being donor atomsthat are coordinated to said transition metal; said cross-bridged chaincomprising from 2 to about 5 atoms.
 2. A metal complex comprising: (A) atransition metal atom selected from the group consisting of Mn(II),Mn(III), Mn(IV), Mn(V), Fe(II), Fe(II), Fe(IV), Co(I), Co(II), Co(III),Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV),Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(II), and Ru(IV);(B) a cross-bridged macropolycyclic ligand comprising: (1) an organicmacrocycle ring comprising: (i) at least 4 donor atoms independentlyselected from the group consisting of N, O, S, and P; 2 to 6 of saiddonor atoms being coordinated to the same transition metal atom; and(ii) a sufficient number of non-donor atoms to separate said donor atomsfrom each other by covalent linkages of at least one non-donor atom; and(2) a moiety that comprises a cross-bridged chain, said cross-bridgedchain comprising from 2 to 5 atoms and covalently connecting at least 2non-adjacent, transition metal atom coordinated, donor atoms of saidorganic macrocycle ring; said cross-bridged macropolycyclic ligand beingcoordinated by at least 4 of said donor atoms to said transition metalatom; and (C) when said cross-bridged macropolycyclic ligand comprisesless than 6 donor atoms coordinated to said transition metal, asufficient number of non-macropolycyclic ligands to complete thecoordination sphere of said transition metal atom; and (D) when saidtransition metals' charge is not neutralized by said non-macropolycyclicligands, a sufficient number of counter ions to provide said metalcomplex with charge neutrality.
 3. The metal complex of claim 2 whereineach counter ion is selected from the group consisting of tosylate, Cl⁻,PF₆ ⁻, ClO₄ ⁻, BF₄ ⁻ and CF₃OSO₃ ⁻.
 4. The metal complex of claim 2comprising one or more transition metal atoms selected from the groupconsisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV)and mixtures thereof.
 5. The metal complex of claim 2 wherein at leastone of said non-macropolycyclic ligands is covalently bound to saidcross-bridged macropolycyclic ligand or at least one of saidnon-macropolycyclic ligands is covalently bound to an alkyl group thatis covalently bound to said cross-bridged macropolycyclic ligand.
 6. Themetal complex of claim 5 wherein at least one of saidnon-macropolycyclic ligands is covalently bound to at least onenon-donor atom of said organic macrocycle ring.
 7. The metal complex ofclaim 5 wherein said non-macropolycyclic ligands are independentlyselected from the group consisting of ROH, NR₃, RCN, RS⁻, RO⁻, RCOO⁻,NR₂H, NRH₂ and RC(O)O⁻ wherein R is substituted alkyl, unsubstitutedalkyl, substituted aryl or unsubstituted aryl; and organic phosphates,organic phosphonates, organic sulfates, organic sulfonates, pyridines,pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines,triazoles, and thiazoles.
 8. The metal complex of claim 2 wherein saidnon-macropolycyclic ligands are independently selected from the groupconsisting of ROH, NR₃, NRH₂, NR₂H, RCN, RS⁻, RO⁻, RCOO⁻, RC(O)O⁻wherein R is substituted alkyl, unsubstituted alkyl, substituted aryl orunsubstituted aryl; and H₂O, OH⁻, OOH⁻, OCN⁻, SCN⁻, N₃ ⁻, CN⁻, F⁻, Cl⁻,Br⁻, I⁻, O₂ ⁻, NO₃ ⁻, NO₂ ⁻, SO₄ ²⁻, SO₃ ²⁻, PO₄ ³⁻, HCO₂ ⁻, NH₃,organic phosphates, organic phosphonates, organic sulfates, organicsulfonates, pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles,pyrimidines, triazoles, and thiazoles.
 9. The metal complex of claim 2comprising from 4 to 6 donor atoms.
 10. The metal complex of claim 2wherein said donor atoms are independently selected from the groupconsisting of N and O.
 11. The metal complex of claim 10 wherein saiddonor atoms are N.
 12. The metal complex of claim 2 wherein at least 3of said donor atoms are N.
 13. The metal complex of claim 2 comprising 4or 5 donor atoms, said donor atoms being coordinated to the sametransition metal atom.
 14. The metal complex of claim 13 comprising 4donor atoms.
 15. The metal complex of claim 13 comprising 5 donor atoms,said donor atoms being N.
 16. The metal complex of claim 2 comprising asingle transition metal atom.
 17. The metal complex of claim 2 whereinat least 4 of the donor atoms in the cross-bridged macropolycyclicligand, form an apical bond angle, D-M-D, with the same transition metalatom, M, of 180±50° and at least one equatorial bond angle, D-M-D, of90±20°.
 18. The metal complex of claim 2 having a coordination geometryselected from the group consisting of distorted octahedral and distortedtrigonal prismatic, and wherein the cross-bridged macropolycyclic ligandis in a folded conformation.
 19. The metal complex of claim 2 wherein 2of the donor atoms in the cross-bridged macropolycyclic ligand occupymutually trans positions with respect to the coordination geometry aboutthe metal, and at least 2 of the donor atoms in the cross-bridgedmacropolycyclic ligand occupy mutually cis-equatorial positions of thecoordination geometry.
 20. The metal complex of claim 2 wherein saidorganic macrocycle ring comprises at least 12 atoms.
 21. The metalcomplex of claim 8 comprising: (a) a single transition metal atomselected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V),Fe(II), Fe(III), and Fe(IV); and (b) said organic macrocycle ringcomprises 4 or 5 donor atoms independently selected from the groupconsisting of N and 0; said donor atoms being coordinated to said singletransition metal atom.
 22. The metal complex of claim 21 comprising: (a)at least one non-macropolycyclic ligand independently selected from thegroup consisting of tosylate, NO₃ ⁻, Cl⁻, Br⁻, H₂O, OH⁻, CH₃C(O)O⁻,HC(O)O⁻, SO₄ ²⁻, PO₄ ³⁻, CH₃OSO³⁻, CH₃CH₂OSO₃ ⁻, CH₃SO₃ and CH₃CH₂SO₃ ⁻;and (b) 2 pendant moieties independently selected from the groupconsisting of methyl, ethyl and propyl; and wherein (c) said organicmacrocycle ring comprises 4 N donor atoms, 2 of said donor atoms beingnon-adjacent bridgehead donor atoms; said donor atoms being separated by2 or 3 non-donor atoms; (d) said pendant moieties are covalently boundto said non-adjacent non-bridgehead N donor atoms; and (e) saidcross-bridged chain is selected from the group consisting of ethylene,propylene, 2-butenylene and o-xylylene.
 23. The metal complex of claim21 comprising at least one non-macropolycyclic ligand independentlyselected from the group consisting of carboxymethyl, 2-hydroxybenzyl and2-picolyl, and wherein (a) said organic macrocycle ring comprises 4 Ndonor atoms, 2 of said donor atoms being non-adjacent bridgehead donoratoms; said donor atoms being separated by 2 or 3 non-donor atoms; (b)said non-macropolycyclic ligand is covalently bound to 1 of saidnon-adjacent non-bridgehead N donor atoms; and (c) said cross-bridgedchain is selected from the group consisting of ethylene, propylene,2-butenylene and o-xylylene.
 24. The metal complex of claim 21 whereinat least one non-macropolycyclic ligand is covalently bound to saidcross-bridged macropolycyclic ligand.
 25. The metal complex of claim 2comprising one or more pendant moieties that are covalently bound tosaid cross-bridged macropolycyclic ligand; one or more of said pendantmoieties being optionally bound to said transition metal.
 26. The metalcomplex of claim 25 wherein said one or more pendant moieties areindependently selected from the group consisting of H, substitutedalkyl, unsubstituted alkyl, substituted aryl or unsubstituted aryl. 27.The metal complex of claim 25 wherein one or more of said pendantmoieties is bound to a donor atom in the organic macrocycle ring. 28.The metal complex of claim 25 comprising one or more transition metalatoms selected from the group consisting of Mn(II), Mn(III), Mn(IV),Mn(V), Fe(II), Fe(III), Fe(IV) and mixtures thereof.
 29. The metalcomplex of claim 25 comprising only one transition metal atom percomplex.
 30. The metal complex of claim 25 comprising a tetradentate orpentadentate cross-bridged macropolycyclic ligand.
 31. The metal complexof claim 25 wherein all the donor atoms in the cross-bridgedmacropolycyclic ligand are selected from the group consisting of N andO.
 32. The metal complex of claim 25 wherein the cross-bridgedmacropolycyclic ligand comprises 4 or 5 donor atoms, all of which arecoordinated to the same transition metal atom.
 33. The metal complex ofclaim 25 wherein the cross-bridged macropolycyclic ligand comprises 4nitrogen donor atoms all of which are coordinated to the same transitionmetal atom.
 34. The metal complex of claim 25 wherein the cross-bridgedmacropolycyclic ligand comprises 5 nitrogen atoms all of which arecoordinated to the same transition metal atom.
 35. The metal complex ofclaim 25 wherein at least 2 of the donor atoms in said metal complex'smacrocycle ring form an apical bond angle, D-M-D, with the sametransition metal atom, M, of 180±50° and at least 2 of which form oneequatorial bond angle of 90±20°.
 36. The metal complex of claim 25having a coordination geometry selected from the group consisting ofdistorted octahedral and distorted trigonal prismatic, and wherein thecross-bridged macropolycyclic ligand is in a folded conformation. 37.The metal complex of claim 25 wherein 2 of the donor atoms in thecross-bridged macropolycyclic ligand occupy mutually trans positions ofthe coordination geometry and at least 2 of the donor atoms in thecross-bridged macropolycyclic ligand, occupy cis-equatorial positions ofthe coordination geometry.
 38. The metal complex of claim 25 comprisingone or two non-macropolycyclic ligands.
 39. The metal complex of claim25 wherein said metal complex's organic macrocycle ring comprises atleast 12 atoms.
 40. A metal complex comprising Mn(II), Mn(III), Mn(IV),or Mn(V); and a cross-bridged ligand having the formula:

wherein in this formula: each “n” is an integer independently selectedfrom 1 and 2, completing the valence of the carbon atom to which the Rmoieties are covalently bonded; each “R” and “R¹” is independentlyselected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl,alkylaryl alkylheteroaryl and heteroaryl, or R and/or R¹ are covalentlybonded to form an aromatic, heteroaromatic, cycloalkyl orheterocycloalkyl ring; said moieties, except for H, being linear orbranched and substituted or unsubstituted; each “a” is an integerindependently selected from 2 or
 3. 41. A metal complex comprisingMn(II), Mn(III), Mn(IV), or Mn(V); and a cross-bridged ligand having theformula:

wherein “R¹” is independently selected from the group consisting of H,C₁-C₂₀ alkyl, alkenyl and alkynyl; said C₁-C₂₀ alkyl, alkenyl andalkynyl moieties being linear or branched and substituted orunsubstituted.
 42. A metal complex comprising a transition metal atomselected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V),Fe(II), Fe(III), Fe(IV), Cr(II), Cr(III), Cr(IV), Cr(V), and Cr(VI); anda cross-bridged ligand having the formula:

wherein m and n are integers from 0 to 2, p is an integer from 1 to 4,and A is a nonhydrogen moiety having no aromatic content.
 43. The metalcomplex according to claim 42 wherein each A is independently selectedfrom the group consisting of methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, C₅-C₂₀ alkyl.
 44. A metal complex comprising atransition metal atom selected from the group consisting of Mn(II),Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Cr(II), Cr(III),Cr(IV), Cr(V), and Cr(VI); and a cross-bridged macropolycyclic ligandhaving the formula:

wherein “R¹” is independently selected from the group consisting of H,C₁-C₂₀ alkyl, alkenyl and alkynyl; said C₁-C₂₀ alkyl, alkenyl andalkynyl moieties being linear or branched and substituted orunsubstituted; R² is selected from the group consisting of ethylene,propylene, 2-butenylene and o-xylylene; and all nitrogen atoms in themacropolycyclic rings are coordinated to the transition metal atom.